MATERIAL SCIENCE AND ENGINEERING

LECTURE (MEMATSCI)
Module 9a- Polymers and Their Properties:
Polymer chemistry, molecular structure
Objectives

• Identify the classification of polymers.

• Understand molecular structure of polymers.
• Name and briefly describe the types of copolymers.
What is a polymer?

Poly mer
many repeat unit

repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP) 3

Adapted from Fig. 14.2, Callister 7e.

Ancient Polymer History
• Originally natural polymers were used
• Wood – Rubber
• Cotton – Wool
• Leather – Silk

• Oldest known uses

• Rubber balls used by Incas
• Noah used pitch (a natural polymer)
for the ark
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C
Saturated hydrocarbons
 Each carbon bonded to four other atoms
H H
H
C C

H H
H

CnH2n+2
Unsaturated Hydrocarbons
Double & triple bonds relatively reactive – can form new bonds
 Double bond – ethylene or ethene - CnH2n

H H
C C
H H
 4-bonds, but only 3 atoms bound to C’s
 Triple bond – acetylene or ethyne - CnH2n-2

H C C H
Isomerism
Isomerism
 two compounds with same chemical formula can have quite different
structures Ex: C8H18
 n-octane

H H H H H H H H
H C C C C C C C C H = H 3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H

 2-methyl-4-ethyl pentane (isooctane) H 3C ( C H 2 ) C H 3

6

CH3
H3C CH CH2 CH CH3
CH2
CH3
Molecular Structures
• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength Adapted from Fig. 14.7, Callister 7e.

Polymers – Molecular Shape
Conformation – Molecular orientation can be changed by rotation around
the bonds
• note: no bond breaking needed

Adapted from Fig. 14.5,

Callister 7e.
Polymers – Molecular Shape
Configurations – to change must break bonds
• Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H

A A

C C
E E
B D D B

mirror plane
Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on same side C C C C C C C C
of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
H R H H H R H H
H H H H H R H H
atactic – R groups random C C C C C C C C
H R H R H H H R
cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same side of chain bulky groups on opposite sides of
chain
Copolymers Adapted from Fig. 14.9,
Callister 7e.

random
two or more monomers polymerized
together
 random – A and B randomly vary in
chain
 alternating – A and B alternate in alternating
polymer chain
 block – large blocks of A alternate bloc
with large blocks of B k
 graft – chains of B grafted on to A
backbone

A– B– graft
DIFFUSION IN POLYMERS
Sample Problem 2
The clear plastic bottles used for carbonated beverages are made from
polyethylene terephthalate (PET). The “fizz ” in the soda results from dissolved
carbon dioxide, and because PET is permeable to CO2, pop stored in PET bottles
will eventually go “flat ”. A 20 oz. bottle of soda has a CO2 pressure of about 400
kPa and the CO2 pressure outside the bottle is 0.40 kPa. Assume that each bottle
has a surface area of 500 cm 2 and a wall thickness of 0.05 cm.
a. Assuming conditions of steady-state, calculate the diffusion flux of CO2 through
the wall of the bottle.
b. If the bottle must lose 750 (cm 3 STP) of CO2 before the soda tastes flat, what is
the shelf-life of the bottle of soda?
Solution:
a. Using the modified equation of Fick’s law of Diffusion and the permeability
coefficient of CO2 through PET from the table, we can have

= =

J=
b. Solving for the time before the soda bottle tastes flat we use the equation for flowrate
Q
DEFECTS IN POLYMERS
Thermoplastics vs. Thermosets
• Thermoplastics:
-- little crosslinking
-- ductile
-- soften upon heating
-- examples:
polyethylene, polypropylene, polycarbonate, polystyrene

• Thermosets:
-- network polymers with significant crosslinking
(10 to 50% of repeat units)
-- harder, stronger and have better dimensional stability
-- do NOT soften upon heating
-- examples:
vulcanized rubber, epoxies,
polyester resin, phenolic resin
Crazing During Fracture of Thermoplastic Polymers
Craze formation prior to cracking

– during crazing, plastic deformation of spherulites

– and formation of microvoids and fibrillar bridges
aligned chains

fibrillar bridges microvoids crac

Fig. 15.9, Callister & Rethwisch 9e. k
(From J. W. S. Hearle, Polymers and Their Properties, Vol. 1, Fundamentals of Structure
and Mechanics, Ellis Horwood, Ltd., Chichester, West Sussex, England, 1982.)
Polymer Additives
Improve mechanical properties, processing, durability, etc.
 Fillers
 Added to improve tensile strength & abrasion resistance, toughness &
decrease cost
 ex: carbon black, silica gel, wood flour, glass, limestone, talc, etc. •
Plasticizers
– Added to reduce the glass transition
temperature
– commonly added to PVC - otherwise it is brittle
Polymer Additives
 Stabilizers
 Antioxidants
 UV protectants

• Lubricants
– Added to allow easier processing
– “slides” through dies easier – ex: Na stearate •
Colorants
– Dyes or pigments
• Flame Retardants
– Cl/F & B
Polymer Types – Fibers
Fibers - length/diameter >100
Primary use is in textiles.
Fiber characteristics:
high tensile strengths
high degree of crystallinity
structures containing polar groups
• Formed by spinning
– extrude polymer through a spinneret (a die
containing many small orifices)
– the spun fibers are drawn under tension
– leads to highly aligned chains - fibrillar structure
Polymer Types – Miscellaneous
• Coatings – thin polymer films applied to surfaces – i.e., paints,
varnishes
• protects from corrosion/degradation
• decorative – improves appearance
• can provide electrical insulation

• Adhesives – bonds two solid materials (adherands)

– bonding types:
1. Secondary – van der Waals forces
2. Mechanical – penetration into pores/crevices
• Films – produced by blown film extrusion
• Foams – gas bubbles incorporated into plastic
 Advanced Polymers
Ultrahigh Molecular Weight Polyethylene (UHMWPE)

• Molecular weight ca. 4 x 106 g/mol

• Outstanding properties
• high impact strength
• resistance to wear/abrasion
• low coefficient of friction UHMWPE
• self-lubricating surface
• Important applications
• bullet-proof vests Adapted from chapter-opening
photograph, Chapter 22, Callister 7e.
• golf ball covers
• hip implants (acetabular cup)
Processing Plastics - Molding
Compression and transfer molding
thermoplastic or thermoset

Adapted from Fig. 15.23, Callister 7e. (Fig.

15.23 is from F.W. Billmeyer, Jr., Textbook
of Polymer Science, 3rd ed.,
John Wiley & Sons, 1984. )
Processing Plastics - Molding
• Injection molding
• thermoplastic & some thermosets

Adapted from Fig. 15.24, Callister 7e. (Fig. 15.24 is from

F.W. Billmeyer, Jr., Textbook of Polymer Science, 2nd
edition,
John Wiley & Sons, 1971. )
Processing Plastics – Extrusion

Adapted from Fig. 15.25, Callister 7e. (Fig. 15.25 is from

Encyclopædia Britannica, 1997.)
Summary
• Polymer applications
-- elastomers -- fibers
-- coatings -- adhesives
-- films -- foams
-- advanced polymeric materials
MATERIAL SCIENCE AND ENGINEERING
LECTURE (MEMATSCI)
Module 10a- Composite Materials and Their
Properties: Introduction
Objectives

• Name the three main divisions of composite materials,

and cite strengthening mechanism and distinguishing
feature of each
• Name the three different types of fiber-reinforced
composites on the basis of fiber length and orientation;
comment on the distinctive and limitations characteristics
for each
• Cite the desirable features of metal-matrix composites
Introduction
• A Composite material is a material system composed of two
or more macro constituents that differ in shape and
chemical composition and which are insoluble in each other.
The history of composite materials dates back to early 20th
century. In 1940, fiber glass was first used to reinforce epoxy.
• Applications:
• Aerospace industry
• Sporting Goods Industry
• Automotive Industry
• Home Appliance Industry
Terminology/Classification

• Composite:
-- Multiphase material that is artificially
made.
• Phase types:
-- Matrix - is continuous
-- Dispersed - is discontinuous a nd
surrounded by matrix

Adapted from Fig. 16.1(a), Callister &

Rethwisch 8e.
Terminology/Classification
• Composites:
woven
-- Multiphase material w/significant proportions of each phase. fibers
• Matrix:
-- The continuous phase
-- Purpose is to:
- transfer stress to other phases 0.5 mm
- protect phases from environment cross
-- Classification: MMC, CMC, PMC section
view
metal ceramic polymer
• Dispersed phase:
-- Purpose: enhance matrix properties. 0.5 mm
MMC: increase y, TS, creep resist. Reprinted with permission from
D. Hull and T.W. Clyne, An Introduction to Composite
CMC: increase K c Materials, 2nd ed., Cambridge University Press, New
PMC: increase E, y, TS, creep resist. York, 1996, Fig. 3.6, p. 47.

-- Classification: Particle, fiber, structural

Advanced Aerospace Application:

Lear Fan 2100 “all-composite” aircraft

Advanced Aerospace Application:
Boeing 767 (and in 777, 787 airplanes w/ the latest, full wing box is
composite):
Composite Design Variations
Classification of Composite Materials
Composites

Particle-reinforced Fiber-reinforced Structural

Large- Dispersion- Continuous Discontinuous Laminates Sandwich

particle strengthened (aligned) (short) panels

Aligned Randomly
oriented

Adapted from Fig. 16.2, Callister

7e.
Composite: Particle-reinforced
Particle-reinforced Fiber-reinforced Structural

Concrete – gravel + sand + cement

(Sand packs into gravel voids)

Reinforced concrete - Reinforce with steel rebar or remesh

- increases strength - even if cement matrix is cracked

Prestressed concrete - remesh under tension during setting of concrete. Tension

release puts concrete under compressive force
- Concrete much stronger under compression.
- Applied tension must exceed compressive force
Post tensioning – tighten nuts to put under rod under tension
but concrete under compression
threaded
nut rod
Classification: Particle-Reinforced

Particle-reinforced Fiber-reinforced Structural

• Examples:
- Spheroidite matrix: particles: Adapted from Fig. 10.19,

steel ferrite () cementite Callister & Rethwisch 8e. (Fig.

10.19 is copyright United
(ductile) ( Fe C ) States Steel Corporation,
3
(brittle) 1971.)
60 m
Adapted from Fig. 16.4,
- WC/Co matrix: particles: Callister & Rethwisch 8e. (Fig.
cemented cobalt WC 16.4 is courtesy Carboloy
Systems, Department, General
(ductile, (brittle,
carbide tough:) hard)
Electric Company.)

600 m
Adapted from Fig. 16.5,
Callister & Rethwisch 8e. (Fig.
- Automobile matrix: particles: 16.5 is courtesy Goodyear Tire
tire rubber rubber and Rubber Company.)
carbon
(compliant)
black
0.75 m (stiff)
Composite: Fiber-reinforced
Particle-reinforced Fiber-reinforced Structural

• Fibers themselves are very strong

– Provide significant strength improvement to material
– Ex: fiber-glass
• Continuous glass filaments in a polymer matrix
• Strength due to fibers
• Polymer simply holds them in place and environmentally protects them
Classification: Fiber-Reinforced

Particle-reinforced Fiber-reinforced Structural

• Fiber Types
– Whiskers - thin single crystals - large length to diameter ratios
• graphite, silicon nitride, silicon carbide
• high crystal perfection – extremely strong, strongest known
• very expensive and difficult to disperse
– Fibers
• polycrystalline or amorphous
• generally polymers or ceramics
• Ex: alumina, aramid, E-glass, boron, UHMWPE

– Wires
• metals – steel, molybdenum, tungsten
Fiber Alignment
Adapted from Fig. 16.8, Callister
7e.

aligned aligned random

continuous discontinuous
Composite: Fiber-reinforced

Particle-reinforced Fiber-reinforced Structur al

• Aligned Continuous fibers
• Examples:
-- Metal: '(Ni3Al)-(Mo) -- Ceramic: Glass w/SiC fibers
by eutectic solidification. formed by glass slurry
matrix:  (Mo) (ductile) Eglass = 76 GPa; ESiC = 400 GPa.

(a) fracture
surface

From F.L. Matthews and R.L. Rawlings, Composite

2 m Materials; Engineering and Science, Reprint ed., CRC
Press, Boca Raton, FL, 2000. (a) Fig. 4.22, p. 145
fibers:  ’ (Ni3Al) (brittle) (b)
(photo by J. Davies); (b) Fig. 11.20, p. 349
(micrograph by H.S. Kim, P.S. Rodgers, and R.D.
Rawlings). Used with permission of CRC
From W. Funk and E. Blank, “Creep deformation of Ni3Al-Mo in-
Press, Boca Raton, FL.
situ composites", Metall. Trans. A Vol. 19(4), pp. 987-998, 1988.
Used with permission.
Composite: Fiber-reinforced

Particle-reinforced Fiber-reinforced Structural

• Discontinuous, random 2D fibers
• Example: Carbon-Carbon
C fibers:
-- process: fiber/pitch, then very stiff
burn out at up to 2500ºC. very strong
(b)
-- uses: disk brakes, gas C matrix:
turbine exhaust flaps, nose less stiff
cones. view onto plane less strong
• Other variations: fibers lie
-- Discontinuous, random 3D (a) in plane
-- Discontinuous, 1D

Ec = EmVm +KEfVf
Composite: Structural

Particle-reinforced Fiber-reinforced Structural

• Stacked and bonded fiber-reinforced sheets
-- stacking sequence: e.g., 0º/90º or 0/45/90º
-- benefit: balanced, in-plane stiffness

• Sandwich panels
-- low density, honeycomb core
Adapted from Fig. 16.16,
-- benefit: light weight, large bending stiffness Callister 7e.

face sheet
adhesive layer
honeycomb

Adapted from Fig. 16.18,

Callister 7e. (Fig. 16.18 is
from Engineered Materials
Handbook, Vol. 1, Composites, ASM International,
Materials Park, OH, 1987.)
•Particulate Methods: Sintering

• Fiber reinforced: Several

•Structural: Usually hand lay-up and atmospheric

curing or vacuum curing
Irwin/McGraw-Hill © 2 0 0 0 Th e Mc G r aw - Hill C o m p a n i e s , Inc.,
Open Mold Processes
Only one mold (male or female) is needed and may be made of any
material such as wood, reinforced plastic or , for longer runs, sheet
metal or electroformed nickel. The final part is usually very smooth.

Shaping. Steps that may be taken for high quality

1. Mold release agent (silicone, polyvinyl alcohol, fluorocarbon, or
sometimes, plastic film) is first applied.
2.Unreinforced surface layer (gel coat) may be deposited for best
surface quality.
Hand Lay-Up: The resin and fiber (or pieces cut from prepreg)
are placed manually, air is expelled with squeegees and if
necessary, multiple layers are built up.
· Hardening is at room temperature but may be improved by heating.
· Void volume is typically 1%.
· Foam cores may be incorporated (and left in the part) for greater shape complexity.
Thus essentially all shapes can be produced.
· Process is slow (deposition rate around 1 kg/h) and labor-intensive.
· Quality is highly dependent on operator skill.
· Extensively used for products such as airframe components, boats, truck bodies,
tanks, swimming pools, and ducts.
SPRAY-UP MOLDING
A spray gun supplying resin in two converging streams into which roving is chopped
· Automation with robots results in highly reproducible production
· Labor costs are lower
Tape-Laying Machines
(Automated Lay-Up)
Cut and lay the ply or prepreg under computer control and without
tension; may allow reentrant shapes to be made.
· Cost is about half of hand lay-up
·Extensively used for products such as airframe components, boats,
truck bodies, tanks, swimming pools, and ducts.
Pultrusion
۰ Fibers are impregnated with a prepolymer, exactly positioned with guides, pulled
through a heated tapering die where curing takes place.

۰Emerging product is cooled and pulled by oscillating clamps

۰Small diameter products are wound up
۰Two dimensional shapes including solid rods, profiles, or hollow tubes, similar to
those produced by extrusion, are made, hence its name ‘pultrusion’
Composite Production Methods
Pultrusion
 Continuous fibers pulled through resin tank, then preforming die & oven to cure

Adapted from Fig. 16.13,

Callister 7e.

۰Production rates around 1 m/min.

۰Applications are to sporting goods (golf club shafts), vehicle drive shafts (because
of the high damping capacity), nonconductive ladder rails for electrical service, and
structural members for vehicle and aerospace applications.
PREPREG PRODUCTION PROCESSES
۰Prepreg is the composite industry’s term for continuous fiber reinforcement pre-
impregnated with a polymer resin that is only partially cured.
۰Prepreg is delivered in tape form to the manufacturer who then molds and fully cures the
product without having to add any resin.
۰This is the composite form most widely used for structural applications
PrePreg Process

• Manufacturing begins by collimating a series of spool-wound

continuous fiber tows.
• Tows are then sandwiched and pressed between sheets of release and
carrier paper using heated rollers (calendering).
• The release paper sheet has been coated with a thin film of heated
resin solution to provide for its thorough impregnation of the fibers.
PrePreg Process
۰The prepreg is stored at 0C (32 F) or lower because thermoset
matrix undergoes curing reactions at room temperature. Also the time
in use at room temperature must be minimized. Life time is about 6
months if properly handled.
۰Both thermoplastic and thermosetting resins are utilized: carbon,
glass, and aramid fibers are the common reinforcements.
۰Actual fabrication begins with the lay-up. Normally a number of plies
are laid up to provide the desired thickness.
۰The lay-up can be by hand or automated.
Summary
• Composites are classified according to:
-- the matrix material (CMC, MMC, PMC)
-- the reinforcement geometry (particles, fibers, layers).
• Composites enhance matrix properties:
-- MMC: enhance y, TS, creep performance
-- CMC: enhance Kc
-- PMC: enhance E, y, TS, creep performance
• Particulate-reinforced:
-- Elastic modulus can be estimated.
-- Properties are isotropic.
• Fiber-reinforced:
-- Elastic modulus and TS can be estimated along fiber
direction
-- Properties can be isotropic or anisotropic.
• Structural:
-- Based on build-up of sandwiches in layered form.