THERMOSETTING

AND THERMOPLSTIC
POLYMERS
Herbert Rathna Singh.G
M.E(MSM)
ANNA UNIVERSITY
 POLYMERS
1. Fundamentals of Polymer Technology
2. Thermoplastic Polymers
3. Thermosetting Polymers
4. Guide to the Processing of Polymers

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Polymer
A compound consisting of long-chain molecules, each
molecule made up of repeating units connected
together
 There may be thousands, even millions of units in a
single polymer molecule
 The word polymer is derived from the Greek words
poly, meaning many, and meros (reduced to mer),
meaning part
 Most polymers are based on carbon and are
therefore considered organic chemicals

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Types of Polymers
 Polymers can be separated into plastics and rubbers
 As engineering materials, it is appropriate to divide
them into the following three categories:
1. Thermoplastic polymers
2. Thermosetting polymers
3. Elastomers
where (1) and (2) are plastics and (3) are rubbers

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Thermoplastic Polymers -
Thermoplastics
Solid materials at room temperature but viscous liquids
when heated to temperatures of only a few hundred
degrees
 This characteristic allows them to be easily and
economically shaped into products
 They can be subjected to heating and cooling cycles
repeatedly without significant degradation
 Symbolized by TP

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Thermosetting Polymers -
Thermosets
 Cannot tolerate repeated heating cycles as
thermoplastics can
 When initially heated, they soften and flow for
molding
 Elevated temperatures also produce a chemical
reaction that hardens the material into an
infusible solid
 If reheated, thermosets degrade and char rather
than soften
 Symbolized by TS

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Market Shares
 Thermoplastics are commercially the most important of
the three types
 About 70% of the tonnage of all synthetic
polymers produced
 Thermosets and elastomers share the remaining
30% about evenly, with a slight edge for the
former
 On a volumetric basis, current annual usage of
polymers exceeds that of metals
Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY
 Examples of Polymers
 Thermoplastics:
 Polyethylene, polyvinylchloride, polypropylene,
polystyrene, and nylon
 Thermosets:
 Phenolics, epoxies, and certain polyesters
 Elastomers:
 Natural rubber (vulcanized)
 Synthetic rubbers, which exceed the tonnage of
natural rubber

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Reasons Why Polymers are
Important
 Plastics can be molded into intricate part shapes,
usually with no further processing
 Very compatible with net shape processing
 On a volumetric basis, polymers:
 Are cost competitive with metals
 Generally require less energy to produce than
metals
 Certain plastics are transparent, which makes them
competitive with glass in some applications

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 General Properties of Polymers

 Low density relative to metals and ceramics

 Good strength-to-weight ratios for certain (but not all)
polymers
 High corrosion resistance
 Low electrical and thermal conductivity

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Limitations of Polymers
 Low strength relative to metals and ceramics
 Low modulus of elasticity (stiffness)
 Service temperatures are limited to only a few
hundred degrees
 Viscoelastic properties, which can be a distinct
limitation in load bearing applications
 Some polymers degrade when subjected to sunlight
and other forms of radiation

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Synthesis of Polymers
 Nearly all polymers used in engineering are synthetic
 They are made by chemical processing
 Polymers are synthesized by joining many small
molecules together into very large molecules, called
macromolecules, that possess a chain-like structure
 The small units, called monomers, are generally
simple unsaturated organic molecules such as
ethylene C2H4

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Polyethylene
 Synthesis of polyethylene from ethylene monomers:
(1)n ethylene monomers, (2a) polyethylene of chain
length n; (2b) concise notation for depicting polymer
structure of chain length n

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Polymerization
 As a chemical process, the synthesis of polymers
can occur by either of two methods:
1. Addition polymerization
2. Step polymerization
 Production of a given polymer is generally
associated with one method or the other

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Addition Polymerization
 In this process, the double bonds between carbon
atoms in the ethylene monomers are induced to open
up so they can join with other monomer molecules
 The connections occur on both ends of the expanding
macromolecule, developing long chains of repeating
mers
 It is initiated using a chemical catalyst to open the
carbon double bond in some of the monomers

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Addition Polymerization
 Model of addition (chain) polymerization: (1) initiation,
(2) rapid addition of monomers, and (3) resulting long
chain polymer molecule with n mers at termination of
reaction

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Step Polymerization
 In this form of polymerization, two reacting monomers
are brought together to form a new molecule of the
desired compound
 As reaction continues, more reactant molecules
combine with the molecules first synthesized to form
polymers of length n = 2, then length n = 3, and so on
 In addition, polymers of length n1 and n2 also combine
to form molecules of length n = n1 + n2, so that two
types of reactions are proceeding simultaneously

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Step Polymerization
 Model of step polymerization showing the two types
of reactions occurring: (left) n-mer attaching a single
monomer to form a (n+1)-mer; and (right) n1-mer
combining with n2-mer to form a (n1+n2)-mer.

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Some Examples
 Polymers produced by addition polymerization:
 Polyethylene, polypropylene, polyvinylchloride,
polyisoprene
 Polymers produced by step polymerization:
 Nylon, polycarbonate, phenol formaldehyde

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Degree of Polymerization
 Since molecules in a given batch of polymerized
material vary in length, n for the batch is an average
 Its statistical distribution is normal
 The mean value of n is called the degree of
polymerization (DP) for the batch
 DP affects properties of the polymer
 Higher DP increases mechanical strength but also
increases viscosity in the fluid state, which makes
processing more difficult

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Molecular Weight
 The sum of the molecular weights of the mers in the
molecule
 MW = n times the molecular weight of each
repeating unit
 Since n varies for different molecules in a batch,
the molecular weight must be interpreted as an
average

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Typical Values of DP and MW

Polymer DP(n) MW

Polyethylene 10,000 300,000

Polyvinylchloride 1,500 100,000
Nylon 120 15,000
Polycarbonate 200 40,000

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Polymer Molecular Structures

 Linear structure – chain-like structure

 Characteristic of thermoplastic polymers
 Branched structure – chain-like but with side
branches
 Also found in thermoplastic polymers
 Cross-linked structure
 Loosely cross-linked, characteristic of
elastomers
 Tightly cross-linked, characteristic of thermosets

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Polymer Molecular Structures

Linear
Branched

Loosely cross-linked Tightly cross-linked

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Effect of Branching on Properties

 Thermoplastic polymers always possess linear or

branched structures, or a mixture of the two
 Branches increase entanglement among the
molecules, which makes the polymer
 Stronger in the solid state
 More viscous at a given temperature in the
plastic or liquid state

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Effect of Cross-Linking on
Properties
 Thermosets possess a high degree of cross-linking;
elastomers possess a low degree of cross-linking
 Thermosets are hard and brittle, while elastomers are
elastic and resilient
 Cross-linking causes the polymer to become
chemically set
 The reaction cannot be reversed
 The polymer structure is permanently changed;
if heated, it degrades or burns rather than melt
Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY
 Crystallinity in Polymers
 Both amorphous and crystalline structures are
possible, although the tendency to crystallize is much
less than for metals or non-glass ceramics
 Not all polymers can form crystals
 For those that can, the degree of crystallinity (the
proportion of crystallized material in the mass) is
always less than 100%

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Crystalline Polymer Structure
 Crystallized regions in a polymer: (a) long molecules
forming crystals randomly mixed in with the
amorphous material; and (b) folded chain lamella, the
typical form of a crystallized region

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Crystallinity and Properties
 As crystallinity is increased in a polymer
 Density increases
 Stiffness, strength, and toughness increases
 Heat resistance increases
 If the polymer is transparent in the amorphous
state, it becomes opaque when partially
crystallized

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Low Density & High Density
Polyethylene

Polyethylene type Low density High density

Degree of crystallinity 55% 92%
Specific gravity 0.92 0.96
Modulus of elasticity 140 MPa 700 MPa
(20,000 lb/in2) (100,000 lb/in2)
Melting temperature 115C 135C
(239F) (275F)

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Some Observations About
Crystallization
 Linear polymers consist of long molecules with
thousands of repeated mers
 Crystallization involves folding back and forth of the
long chains upon themselves
 The crystallized regions are called crystallites
 Crystallites take the form of lamellae randomly mixed in
with amorphous material
 A crystallized polymer is a two-phase system
 Crystallites interspersed in an amorphous matrix

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Factors for Crystallization
 Slower cooling promotes crystal formation and growth
 Mechanical deformation, as in the stretching of a
heated thermoplastic, tends to align the structure and
increase crystallization
 Plasticizers (chemicals added to a polymer to soften
it) reduce crystallinity

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Thermal Behavior of Polymers

 Specific volume
(density)-1 as a
function of
temperature

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Additives
 Properties of a polymer can often be beneficially
changed by combining it with additives
 Additives either alter the molecular structure or
 Add a second phase, in effect transforming the
polymer into a composite material

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Types of Additives by Function

 Fillers – strengthen polymer or reduce cost

 Plasticizers – soften polymer and improve flow
 Colorants – pigments or dyes
 Lubricants – reduce friction and improve flow
 Flame retardents – reduce flammability of polymer
 Cross-linking agents – for thermosets and elastomers
 Ultraviolet light absorbers – reduce degradation from
sunlight
 Antioxidants – reduce oxidation damage

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Thermoplastic Polymers (TP)
 Thermoplastic polymers can be heated from solid state
to viscous liquid and then cooled back down to solid
 Heating and cooling can be repeated many times
without degrading the polymer
 Reason: TP polymers consist of linear and/or
branched macromolecules that do not cross-link
upon heating
 Thermosets and elastomers change chemically when
heated, which cross-links their molecules and
permanently sets these polymers
Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY
 Mechanical Properties of
Thermoplastics
 Low modulus of elasticity (stiffness)
 E is much lower than metals and ceramics
 Low tensile strength
 TS is about 10% of metal
 Much lower hardness than metals or ceramics
 Greater ductility on average

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Strength vs. Temperature
 Deformation
resistance
(strength) of
polymers as a
function of
temperature

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Physical Properties of
Thermoplastics
 Lower densities than metals or ceramics
 Typical specific gravity for polymers are 1.2
(compared to ceramics (~ 2.5) and metals (~ 7)
 Much higher coefficient of thermal expansion
 Roughly five times the value for metals and 10
times the value for ceramics
 Much lower melting temperatures
 Insulating electrical properties
 Higher specific heats than metals and ceramics

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Commercial Thermoplastic
Products and Raw Materials
 Thermoplastic products include
 Molded and extruded items
 Fibers and filaments
 Films and sheets
 Packaging materials
 Paints and varnishes
 Starting plastic materials are normally supplied to the
fabricator in the form of powders or pellets in bags,
drums, or larger loads by truck or rail car

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

Applications of Thermoplastic (TP)
• They are useful for a variety of applications, including consumer
goods, machine parts and packaging and storage materials.
• Acrylic - It serves as a sturdy substitute for glass for such items as
aquariums, motorcycle helmet visors, aircraft windows, viewing
ports of submersibles, and lenses of exterior lights of automobiles
• Nylon - Nylon fibers are useful in making fabrics, rope, carpets and
strings for musical instruments
• Polypropylene - Polypropylene (PP) is useful for such diverse
products as reusable plastic containers, diapers, sanitary pads, ropes,
carpets, plastic moldings, piping systems, car batteries.
• Teflon - Teflon is the brand name given by DuPont Corp. for a
polymer called polytetrafluoroethylene (PTFE), which belongs to a
class of thermoplastics known as fluoropolymers. It is famous as a
coating for non-stick cookware.
 Thermosetting Polymers (TS)
 TS polymers are distinguished by their highly
cross-linked three-dimensional, covalently-bonded
structure
 Chemical reactions associated with cross-linking are
called curing or setting
 In effect, formed part (e.g., pot handle, electrical
switch cover, etc.) becomes a large macromolecule
 Always amorphous and exhibits no glass transition
temperature

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 General Properties of
Thermosets

 Rigid - modulus of elasticity is two to three times

greater than thermoplastics
 Brittle, virtually no ductility
 Less soluble in common solvents than thermoplastics
 Capable of higher service temperatures than
thermoplastics
 Cannot be remelted - instead they degrade or burn

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Cross-Linking in TS Polymers

 Three categories:
1. Temperature-activated systems
2. Catalyst-activated systems
3. Mixing-activated systems
 Curing is accomplished at the fabrication plants that
make the parts rather than the chemical plants that
supply the starting materials to the fabricator

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Temperature-Activated Systems

Curing caused by heat supplied during part shaping

operation (e.g., molding)
 Starting material is a linear polymer in granular form
supplied by the chemical plant
 As heat is added, material softens for molding,
but continued heating causes cross-linking
 Most common TS systems
 The term “thermoset" applies best to these
polymers

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Catalyst-Activated Systems
Cross-linking occurs when small amounts of a catalyst
are added to the polymer, which is in liquid form
 Without the catalyst, the polymer remains stable and
liquid
 Once combined with the catalyst it cures and
changes into solid form

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 Mixing-Activated Systems
Mixing of two chemicals results in a reaction that forms
a cross-linked solid polymer
 Elevated temperatures are sometimes used to
accelerate the reactions
 Most epoxies are examples of these systems

Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY

 TS vs. TP Polymers
 TS plastics are not as widely used as the TP
 One reason is the added processing costs and
complications involved in curing
 Largest market share of TS = phenolic resins with 
6% of the total plastics market
 Compare polyethylene with  35% market share
 TS Products: countertops, plywood adhesives, paints,
molded parts, printed circuit boards and other fiber
reinforced plastics
Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY
Applications of Thermosetting (TS)
• Epoxies :
 Characteristics: Excellent combination of mechanical
properties and corrosion resistance; dimensionally stable;
good adhesion; relatively inexpensive; good electrical
properties.
 Application: Electrical moldings, sinks, adhesives, protective
coatings, used with fiberglass laminates.
• Phenolics :
 Characteristics: Excellent thermal stability to over 150o C; may
be compounded with a large number of resins, fillers, etc.;
inexpensive.
 Application: Motor housing, telephones, auto distributors,
electrical fixtures
 Guide to the
Processing of Polymers

 Polymers are nearly always shaped in a heated,

highly plastic state
 Common operations are extrusion and molding
 Molding of thermosets is more complicated because of
cross-linking
 Thermoplastics are easier to mold and a greater
variety of molding operations are available
 Rubber processing has a longer history than plastics, and
rubber industries are traditionally separated from plastics
industry, even though processing is similar
Herbert Rathna Singh.G ,(M.E) MSM, ANNA UNIVERSITY
 Reference
• https://nptel.ac.in/courses/112108150/pdf/Lecture_Notes/MLN_11.pdf
• https://ed.iitm.ac.in/~shankar_sj/Courses/ED5312/Materials_for_Automo
biles17.pdf
• https://www.e-education.psu.edu/matse81/node/2209
• https://www.modorplastics.com/plastics-learning-center/thermoset-vs-
thermoplastics/
• https://www.osborneindustries.com/news/thermosetting-plastic-uses-
applications/
• https://www.wur.nl/web/file?uuid=8ae7bb81-a554-4df3-9396-
aef22860c845&owner=12587277-d675-4ba5-b76e-045bd049bd35
• https://www.youtube.com/watch?v=4fTtrKPySm0
• https://www.slideshare.net/herberthrssing
THANK YOU.