Unit 2 Polymer and Composites

INTRODUCTION

 Polymers are macromolecules formed by linking of many small molecules.

 The polymers are giant molecules with high molecular masses.
 The single repeating unit is called as monomer, and the resultant high molecular weight compound
is called as polymer.
 For example, the monomer ethylene gets linked with many other ethylene molecules to form
polyethylene.
CLASSIFICATION OF POLYMER
Classification Based on Chemical Structure
Classification Based on Arrangement of Monomers
Glass Transition Temperature (Tg)
 What is glass transition temperature (Tg)?

 Tg is the temperature at which an amorphous polymer changes from a hard/glassy state to a soft/leathery state, or
vice versa.
 An important feature of polymer behavior.
 Changes in the physical and mechanical properties.

Below Tg: Due to lack of mobility, the polymers are hard and brittle like glass.

Above Tg: Due to some mobility, the polymers are soft and flexible like rubber.
 Applications and Importance of Tg:

1. Materials Behavior: Tg impacts the behavior of polymers. Below Tg, the material is glassy and
rigid, while above Tg, it becomes rubbery or viscous.

2. Processing and Manufacturing: Tg influences the processing conditions for polymers. For
instance, during molding or extrusion, knowing Tg helps optimize temperature and cooling rates.

3. Stability and Controlled Properties: Many industries require materials with stable and controlled
Tg values. These include aerospace, automotive, electronics, and packaging.

4. Design Optimization: Understanding Tg aids in designing materials with desired properties. For
example, selecting a polymer with an appropriate Tg ensures optimal performance in specific
applications.

5. Thermal Expansion and Viscosity: Tg affects thermal expansion, viscosity, and other physical
characteristics of materials.
Factors Affecting Glass Transition Temperature (Tg):
 Degree of Polymerization (Dp)

No. of monomer units present

Degree of Polymerization (Dp)
in a polymer

Where Dp is the degree of polymerization,

M is the molar mass of the polymer and
m is the molar mass of the monomer unit.

 High degrees of polymerization indicate long polymer chains and complex structures.

 Low degrees suggest short chains and simpler structures

Polymer Molecular Weight
What is Number Average Molecular Weight?

 Number average molecular weight is the mole fraction of molecules in a polymer sample.

 It is a way of determining the molecular mass of a polymer.

 It gives the average of the molecular masses of the individual macromolecules.

 In other words, it is the total weight of the sample divided by the number of molecules in the sample.

Figure: Mw > Mn
What is Weight Average Molecular Weight?

 Weight average molecular weight is the weight fraction of molecules in a polymer sample.

 It is another way of determining the molecular mass of a polymer.

 It gives the average of the molecular masses of the individual macromolecules in the polymer sample.

Where, n=Moles of molecules (n1+n2+n3+----------ni)

M=Molecular weight of each molecule

Difference Between Number Average and Weight Average Molecular Weight

 The key difference between number average and weight average molecular weight is that the number
average molecular weight refers to the mole fraction of molecules in a polymer sample whereas the weight
average molecular weight is the weight fraction of molecules in a polymer sample.

 We can determine the number average molecular weight using gel permeation chromatography, viscometry
and colligative methods such as vapour pressure osmometry

 We can determine the weight average molecular weight using static light scattering, small angle neutron
scattering, X-ray scattering, and sedimentation velocity.
Numericals:
 Mechanism

It can be done by 4 Mechanisms:

• Cationic Polymerization
• Anionic Polymerization
• Free Radical Polymerization
• Coordination Polymerization or Ziegler-Natta Polymerization
 Commercial Polymers

1. POLYETHYLENE (PE)

2. POLYPROPYLENE (PP)

3. POLYVINYL CHLORIDE (PVC)

4. POLYSTYRENE (PS)

5. PHENOL FORMALDEHYDE (PF)

6. EPOXY RESIN
 Commercial Polymers

1. Polyethylene (PE):

Synthesis:  PE is obtained by the polymerization of ethylene.

 The gas is first liquefied under high pressure (upto 1500 atm) and then pumped into a
heated pressure vessel, maintained at 150 to 250oC.
 By catalytic effects of traces of oxygen present, ethylene is polymerized into polyethylene.
 A Waxy solid is formed at the bottom of the vessel.

By using free radical initiator LDPE is obtained

By using Ionic catalyst HDPE is obtained.
 better packing density

mp
Properties: 1. Depending upon the density, they may be LDPE and HDPE.
2. If we use free radical initiator, LDPE is the product while use of ionic catalysts results in the
formation of HDPE.
3. It is a rigid, waxy white solid. Translucent.
4. It is permeable to many organic solvents.
5. It crystallizes easily.

Uses: 1. These are useful in the preparation of insulator parts, bottle caps, flexible bottles, pipes etc.
2. LDPE is used in making film and sheeting.
3. Pipes made of LDPE are used for both agricultural, irrigation and domestic water
line connections.
4. HDPE is used in manufacture of toys and other household articles.
2. Polypropylene (PP):

Synthesis: It is obtained by polymerizing propylene in presence of Ziegler-Natta Catalyst (AlR3-

AlCl3)

Properties:  PP is stereoregular (isotactic) and highly crystalline polymer

(mp= 160-170oC.
 It possess better hardness, strength and stiffness than PE.
 It is more resistant that PE.
Uses:
 In producing moulded parts and fibres.

 Its fibres are used in making ropes (extremely strong by weight), carpets (indoor as well as
outdoor purposes), blankets, hand bags, etc.

 Used for making water pipes, washing machine parts, serializable hospital equipment, etc.
3. Poly Vinyl Chloride (PVC):

Synthesis: It is obtained by heating a water-emulsion of Vinyl Chloride in presence of small

amount of Benzyl Peroxide or Hydrogen Peroxide in an autoclave under pressure.
Properties:  PVC is colorless, odourless, noninflammable, and chemically inert powder, resistant to light,
atmospheric oxygen, etc.
 Pure resin possesses a high softening point (145oC) and a greater stiffness and rigidity
compared to PE, but is brittle.

Uses:  It is used for making sheets, which are employed for light fitting, safety helmets, motorcycle
mudguards, pipes, bottle, etc.
4. POLYSTYRENE (PS)

Synthesis: It is prepared by polymerization of styrene (dissolved in ethyl benzene) in the presence of

benzoyl peroxide catalyst
Properties:
1. PS is a transparent, light, excellent moisture resistant
2. It can be nitrated by fuming nitric acid and sulfonated by conc. H2SO4
3. At above 100oC, it yields water-soluble emulsion.
4. It is highly electric insulating, highly resistant to acid and good chemical resistant.
5. It has relatively low softening range (90-100oC) & is brittle.

Uses: In the molding of articles like toys, combs, radio & television parts, refrigerator parts,
battery cases, high-frequency electric insulators, lenses, indoor lighting panels, etc.
5. PHENOL FORMALDEHYDE (PF)

When two monoethylol phenols react with each other, Novolac resin is produced by the elimination of a water
molecule. Novolac resin is also referred to as phenol-formaldehyde resin.

The Novolac resin is further heated in the availability of formaldehyde which leads to the formation of a
cross linked polymer which is referred to as Bakelite.
 Uses:

 automotive and woodworking industries.

 Automotive components such: as brake pads, fuel pumps, and transmission parts are
all made with phenolic-based resins.

 In the woodworking space, phenol formaldehyde is sometimes used in the

manufacturing of medium-density fiberboard and particleboard. Those materials find
application in furniture making, cabinetry, and flooring products.

 The function of the resin is to create a strong and durable bond between the wood
fibers. The resulting bond is impervious to moisture and insects. It is a valuable resin
that is essential to many industrial processes.
6. EPOXY RESIN
Synthesis:
It is a combination of Bisphenol and Epichlorohydrin
Properties:
 Resistance to chemicals, particularly alkaline environments.
 Heat resistance.
 Adhesion to a variety of substrates.
 High tensile, compression, and bend strengths.
 Low shrinkage during curing.
 High electrical insulation and retention properties.
 Corrosion resistance.
Uses:
 Conductive Polymers:
 Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic
polymers that conduct electricity.

 They have alternating single and double bonds along the polymer backbone (conjugated
bonds).

 It is composed of aromatic rings such as Phenylene, naphthalene, anthracene, pyrrole, and

thiophene, which are connected through carbon-carbon single bonds.

 The biggest advantage of conductive polymers is their processability, mainly by dispersion.

 The conduction of polymer may be due to unsaturation or due to the presence of externally
added ingredients in them.
 Conductivity

 Polymers become conducting upon doping

 Polymer becomes electronically charged

 Polymer chains generate charge carriers

 The concentration of dopant causes certain

electrons to become unpaired

 Formation of polarons and bipolarons

CP Examples:
Classification of conducting polymers
Intrinsically conducting polymers are substances which have a π-bоnd backbone.
 There are certain electrons which are extra in this type of polymers.
 These extra electrons flow from one point to another in the polymer, as a result they have the ability to
conduct electricity.
 Conduction of electricity in this type of polymers is due to conjugation in the backbone of polymer.
 The conjugation can be due to either electrons or due to doped ingredients.

Conduction due to conjugated π electrons:

 The presence of double bonds and lone pair of electrons conduction of electricity takes place.
 Due to the overlapping of conjugated π electrons, valence and conduction bands throughout the backbone of
the polymer are developed.
 Electrical conduction can occur only after the attainment of the required energy of activation, either thermally
or photochemically, because there is some gap between the valence and conduction bands.
 Polyacetylene, polyaniline, etc., are these types of conducting polymers.
Doped Conducting Polymers

 The conduction power of semiconductor can be enhanced by adding some foreign material or desired impurities.

 These impurities are called doping agent or dopant.

 Appropriate doping agent increase the conductivity of semiconductors up to 104 times.

 The increase in conduction is due to the participation of impurity elements in between the valence band and
conduction band.

 Making a bridge through which electrons can jump easily from the valence band to the conduction band.
The foreign materials develop positive or negative charge through oxidation or reduction of the semiconductor.

Doping are mainly two types.

1. p-type doping through oxidation of materials:

 Some electrons from the conjugated π bonds are removed through oxidation creating a positive hole called polaron
inside the polymer.
 The positive hole or polaron can move throughout the polymeric chain and make it conducting polymer.
2. n-type doping through reduction of materials:
 Some electrons are introduced to the conjugated π bonds through reduction creating a negative hole or charge
inside the polymer.
 The negative hole or charge can move throughout the polymeric chain and make it conducting polymer.
 Lewis bases, are generally used as doping agents.
 Biodegradable Polymers
 Polymers which get degraded into simple molecules like CO2, water, methane, inorganic
compounds, biomass, etc. under aerobic or anaerobic environment by the action of
microorganisms or enzymes.

 Polymers comprised of monomers linked to one another through functional groups and have unstable links
in the backbone
Factors affecting Biodegradation of Polymers
 Based on biodegradability polymers are classified as:

1. Biodegradable polymers

e.g.: poly glycolic acid, Poly lactic acid etc.

2. Non biodegradable polymers

e.g.: poly vinyl chloride, polyethylene etc.

Classification of biodegradable polymers based on the source

1) Synthetic biodegradable polymers:

e.g.: Aliphatic poly(esters), Polyanhydrides, Polyphosphazenes, polyaminoacids, etc.

2) Natural biodegradable polymers:

e.g: Albumin, Collagen, Dextran, Gelatin, starch etc.

Examples:
1. Poly-3-hydroxyl butyrate-co-3-hydroxyl valerate (PHBV)

+
2. Polylactic acid (PLA):

Synthesis:
3. Polyglycolic Acid (PGA):
4. Nylon-2 Nylon-6
 Properties:

 Degradation usually starts at the end groups because BDP have exceptionaly strong carbon backbones
that are difficult to crack.

 BDP can maintain strong mechanical integrity until they are degraded.

 Non-toxix

 The degradation rate can be controlled

 Hydrophilic polymers
 Uses:

 Used for stitches after surgery

 Utilized in agriculture goods like seed coating and films

 In gene therapy

 These are employed in medicinal agents such as anticancer, antipsychotic, and anti-
inflammatory drugs in the biodegradable system.

 Fast-food packaging & personal hygiene items.

 Composites
 A composite material (composites) is a material that consists of two or more discontinuous
components (particles/fibers) that are placed in a continuous medium (matrix).

Characteristics:
 In a fiber composites the matrix binds together the fibres, transfer loads between the fibers and protects them
from environment and external damage.

Examples:

1. Wood: Cellulose fibers bound by lignin matrix

2. Granite: Quartz, feldspar and mica

3. Concrete: Cement, water, sand, gravel

Constituents of Composites:

1. Matrix Phase : Continuous body constituent which encloses the composite and gives
its bulk form e,g, polymer

2. Dispersed phase: Structural constituent which determines internal structure of the

composite. Fibres, particulate, flakes, etc.
A. Fiber-reinforced composites (FRC):

 Dispersed phase: fiber e.g. carbon, glass, etc.

 Continuous phase: polymer.

 FRC possesses high specific strength, stiffness, corrosion resistance and lower density

The mechanical characteristics of FRC depend on:

 Properties of fiber

 Interfacial bond between fiber and matrix

 Fiber length like longer gives continuous, and shorter length gives discontinuous or random.

 The reinforcement efficiency of continuous fibers is higher than short fibers

 Fiber orientation & concentration i.e. if it is orderly oriented and continuous it is highly

anisotropic or discontinuous or random orientation

General Properties of Composites

 High Strength to weight Ratio

 Lightweight

 Fire Resistance

 Electrical Properties

 Chemical and weathering resistance

 Color

 Translucency

 Design

 Low Thermal Conductivity Manufacturing Economy

Examples:
1. Glass fiber reinforced polymer composites: glass fiber + plastic matrix
2. Carbon fiber reinforced polymer composites: carbon fiber like graphite, graphenes, CNTs + polymer matrix
3. Alumina Oxide/carbon fiber reinforced metal composites: Fiber of alumina (Al2O3)/Carbon in metal or
metal alloy matrix

B. Particle (particulate) reinforced composites (PRC)

Solid particles of metal oxides or carbides of varying sizes are dispersed in metal, metal alloy, ceramic, or
polymer matrix.
PRC is classified into two types:
1. Large particulate composites
2. Dispersed strengthened composites
1. Large particulate composites:
It is used with all three major types of materials: metal, polymer, and ceramics.
Examples:
1. Concrete: Cement matrix and particulates of sand and gravel
2. Automobile tire: carbon black particles dispersed in rubber matrix

2. Dispersed strengthened composites

 Very small particles in the range of 10-100nm size are used.
 It improves strength and hardness.
 Example: Thoria-dispersed nickel: used in various high temp.
operations like combustion engines
C. Structural Composites:

 prepared by compressing the stacking of layers of fiber-reinforced composites.

 Types: Laminated and sandwich

Applications of Composite Materials

1. Aircraft Industries
 Applications of Composite Materials

1. Aeronautical applications: Structural components like wings, body & stabilizer & fuel

of aircraft, rocket army missiles in military, etc.

2. Automobile industries: Automobile parts like components of the engine, spray

nozzle, mudguards, tires, etc.

3. Communication industry: preparation of antennae and electronic circuit boards.

4. Safety equipment: helmets.

5. Marine applications: Shaft, hulls, and other parts of ships.

6. Sports equipment: tennis rockets and golf sticks.

Disadvantages & Limitations of Composite Materials