MAE 3344-001

Introduction to Manufacturing Engineering

Polymers: Chapter 07

Sunand Santhanagopalan
Multi-Scale Energy Systems (MuSES) Laboratory
Mechanical & Aerospace Engineering University
of Texas at Arlington
 Characteristics of Polymers 2

Advantages Limitations
• Ease of manufacture • Low strength, stiffness
• Relatively low cost • High coefficient of thermal expansion
• Complexity of design possibilities • Low useful temperature range
• Corrosion, chemical resistance • Low dimensional stability over time
• Low electrical and thermal • Impact Performance
conductivity
• Low density
• High strength-to-weight ratio
(reinforced)
• Noise reduction
• Wide choice of colors and
transparencies
• Minimal polishing needed
Different Polymers and Properties 3
Different Polymers and Properties 4
 Polymer Structure 5

• Properties depend on polymer

molecules
• shape,
• size,
• arrangement
• Long chain molecules
• Monomer – basic building block
How are Polymers made? 6
 Polymerization 7

• Condensation polymerization (Step growth)

• Reaction by-products condensed out
• Polymer molecule grows step-by-step until all of one reactant consumed
• Addition polymerization (Chain growth)
• No reaction by-products
• Initiator added to open double bond between two carbon atoms to begin linking
process
• Long molecules form at high rate
 Characteristics of Polymerization 8

• Molecular weight
• Higher molecular weight: greater average chain
length
• Strong influence on properties

• Degree of polymerization
• Ratio of molecular weight of polymer to that of
repeating unit
• Higher DP: higher viscosity and strength

• Bonding
• Primary bonds: covalent bonds (monomers)
• Secondary bonds: van der Waals, hydrogen –
m10x-100x weaker (polymer chains)
• Longer polymer chain—greater energy needed to
overcome secondary bond strength
 Characteristics of Polymerization 9

• Linear
• Branched
• Cross-linked Thermoplastics
• Network
• Copolymers &
Terpolymers

Thermosets
 Crystallinity of Polymers 10

• Amorphous (spaghetti bowl)

• Can impart crystallinity

• Crystallites: 2-phase material (semicrystalline)
• Linear: can become highly crystalline
• Highly branched—only low degree of crystallinity

• Affects properties
• More crystallization—
• stiffer, harder, less ductile
• more dense, less rubbery
• more resistant to solvents and heat
• Optical properties—opaqueness, index of
refraction
 Glass Transition Temperature 11

• Amorphous polymers
• No sharp melting point
• Distinct change in mechanical properties across narrow temperature range
• Low temperature—hard, rigid, brittle
• High temperature—rubbery, leathery
 Thermoplastics 12

• Linear and branched polymers

• weak secondary bonds
• determines overall strength of polymer

• Weaken secondary bonds above Tg or Tm

• adjacent polymer chains can move
• easier to shape, mold

• Reversible process
• cool polymer
• return to original hardness and strength
Thermoplastic – Nylon, PTFE
• Examples: Acetals, Acrylics, Cellulosics,
Polyamides, Polycarbonates, Polyesters, Thermosets - Phenolic
Polystyrenes etc.
 Thermoplastics: Temperature Effects 13

• First leathery, then viscous fluid

• Can be molded and solidified – can cause
thermal aging
• Strength, stiffness decrease; ductility
increases

Cellulose acetate
 Thermoplastics: Strain Rate Effects 14

• Similar to metals
• Strain rate sensitive

• High m
• Long elongation before necking
and fracture

• Effect of Orientation
• alignment of molecule chains
under deformation
• becomes anisotropic

Large uniform deformation—e.g. stretch

plastic holder on 6-pack
 Thermoplastics: Other Factors 15

• Stress and creep relaxation at room temperature

• Crazing
• localized, wedge-shaped, narrow regions of highly deformed material
• Spongy, 50% voids.
• under tensile, bending stress
• Stress-whitening

• Hygroscopic—absorb water
• dimensional changes, lower yield stress, elastic modulus, Tg

• Low thermal, electrical conductivity

• Low specific gravity (density relative to water)— 0.90 to 2.2

• High coefficient of thermal expansion

 Thermosetting Plastics 16

• Cross-linking effectively produces one giant molecule

• Irreversible process—permanently set
• Staged manufacturing process
• First stage—partial polymerization at chemical plant
• Second stage—cross-linking during part production
• Relative to thermoplastics
• Better mechanical, thermal, and chemical properties
• Better electrical resistance,
• Better dimensional stability
• Tg not sharply defined
• Strength, hardness not as sensitive to temperature, deformation rate
• Examples: Aminos, Epoxies, Phenolics, Alkyds, Silicones etc.
 Elastomers 17

• Rubber
• Amorphous polymers
• undergo large elastic deformation without rupture
• Soft
• Low elastic modulus
• Low Tg
• Can be cross-linked (vulcanization) but can’t be reshaped

Hysteresis—energy absorption
General Properties 18
 Additives in plastics 19

• Plasticizers
• impart flexibility, softness by lowering Tg; reduce secondary bond strength
• Fillers
• particles, fibers—reduce cost, improve properties
• Colorants
• dyes, pigments
• Flame retardants
• Lubricants
• Additives for protection from UV radiation and oxidation degradation
 Recap: Chapter 7 20

• Polymer Structure • Thermoplastics

• Monomers to polymers • Linear and Branched
• Covalent and secondary bonds • Semi-crystalline or
Amorphous
• Polymerizartion? • Easy to shape, mold
• Condensation – by proucts • Temperature effects
• Addition – no by products • Glassy to viscous fluid
• Molecular weight • Strain rate effects
• Degree of polymerization
• Thermsets
• Polymer chains • Cross linked or network
• Linear • Amorphous mostly
• Branched • No sharp Tg
• Crosslinked • Permanently set
• Netowrk
• Elastomers
• Crystallinity • Rubber
• Amorphous • Soft and large elastic
• Semi Crystalline deformation

• Glass Transition Temperature

 21
Questions
• Are polymers more or less impact resistant than metals?
• Does polymer chain length affect molecular weight?
• Is polymerization the same as crosslinking?
• Why are longer chain polymer less easy to break? Primary or secondary bonds?
• Can polymer be completely crystalline?
• More crystallization – More brittle or ductile. Why?
• Do thermoplastics withstand higher stress before fracture as opposed to
thermosets?
• Does high m (strain rate sensitivity) mean more elongation before fracture. Is
this similar to metals?
• What is crazing?
• Why are thermosets less sensitive to temperature?
• Can hysteresis in elastomers be useful?