Composites

Composites
• Very important in our 21st Century world
• Listed as one of the top 10 greatest
engineering developments of last quarter
of the 20th Century
– Others: Apollo moon landing, unmanned
satellites, microprocessor, computer aided
design (CAD), CT scan, jumbo jet, lasers,
fiber-optic communication, genetic
engineering
 What are composites?
• Solid materials composed of a binder or
matrix that surrounds and holds in place
reinforcements.
– The material consists of two (or more) phases
– One of the phases is continuous (the matrix)
– The other phase is discontinuous (the
reinforcement)
– The phases can be thought of as a group of
islands (discontinuous) in a sea (continuous)
 Composites Offer
High Strength
Light Weight
Design Flexibility
Consolidation of Parts
Net Shape Manufacturing
 Constituents of composite materials

1. Matrix phase
Continuous phase, the primary phase.
It holds the dispersed phase and shares a load with it.

2. Dispersed (reinforcing) phase

The second phase (or phases) is imbedded in the matrix in a
continuous/discontinuous form.
Dispersed phase is usually stronger than the matrix, therefore it is sometimes
called reinforcing phase.

3. Interface
Zone across which matrix and reinforcing phases interact (chemical, physical,
mechanical)
 Matrix purposes
• Hold the reinforcements together
• Give shape to the object
• Transfer loads to the reinforcements
Protect the reinforcements
– Heat
– Weather
– Flammability
– Impacts
– Solvent/water
 Reinforcement purposes
• Carry the load (most mechanical
properties)
• Give directionality of some properties
(optional)
 Interface: Function

• To transfer the stress from matrix to

reinforcement

Sometimes surface treatment is carried out

to achieve the required bonding to the matrix
Interface
The interface is the surface between the
reinforcement and the matrix that determines the
stress transfer process of the matrix-
reinforcement-matrix, which affects on :
- specific strength
- specific stiffness
- fracture toughness
- creep endurance
Types of interfacial bonding:
• Molecule entanglement → the existence
of bonds between molecules on the
surface of reinforce (e.g. fiber) and matrix.
• Electrostatic → different atomic charge
between the reinforce and the matrix on
the interface surface which results in
attraction, if there is gas, the bond
weakens.
• Chemical reaction at the interface
there are some functional group which
may be bonded each other between
reinforcement and dan matrix
• Mechanical bonding  the existence of
interlocking mechanism on the surface, so
the more coarse surface the stronger the
bond between reinforcement and matrix
 Basic Materials – a primer
• Three types of solid materials
– Ceramics
– Metals
– Polymers
• These differ, at the most fundamental
level, in the types of bonds between the
atoms
Periodic Table of the Elements
Metals Non-Metals
Ceramics Polymers
(Ionic Bonds) (Covalent Bonds)

Metals
(Metallic Bonds)
 Polymers
• Polymers can be natural (like wood,
cotton, wool, leather)
• Polymers can be man-made (plastics)
• Polymers can be easily shaped (molded)
• Polymers have other advantages over
ceramics and metals
Physical Properties of Polymers
• Composed of very large molecules
• Low modulus of elasticity (low stiffness)
• Low tensile and compressive strengths
• Can be crystalline or semi-crystalline structure
• Deformation is very sensitive to temperature
• Low thermal and electrical conductivity (good
insulator)
• Low temperatures make plastics brittle
• Plastic deformation
Advantages of Polymers (over metals or ceramics)
• Low density (specific gravity = 1.0 – 1.4) (7.85 for
steel)
• Corrosion resistance
• Easy to manufacture, easy to make complex
shapes (low temperature to shape)
• Electrical insulation
• Low thermal conductivity
• Low finishing cost (no painting)
• Toughness, ductility
• Optics ( can be transparent) (preferred to glass
because of light weight and toughness) (aircraft
windows are plastics)
Disadvantages of Polymers (relative to metals or
ceramics)
• Low use temperature
• Time-temperature dependence of properties.
• Low stiffness (Modulus, E  E of a metal/100)
• Low strength (strength might be improved using
composite structures)
• May swell with water
• Toxicity, flammability
• Solvent sensitivity (may be soluble or properties
may change)
• U.V. light sensitivity (can break covalent bonds for
some polymers)
Types of polymer:
• Homopolymers: made up from only 1 type of
monomer.
• Copolymers: made up of 2 or more types of
chemically distinct monomers.

Copolymer
- Made up of 2 or more types of chemically distinct
monomers.
- It may be composed of two bifunctional units and may
alternate to give a well-defined recurring unit or the two
different monomers may be joined in a random fashion
in which no recurring unit can be defined.
- Synthetic rubbers are often copolymers,
e.g., SBR – styrene butadiene rubber (used in automobile tires) is a
random copolymer.
Alternating copolymer:
A copolymerization involving monomers A
and B that results in -A-B-A-B-A-.

Random copolymer:
A copolymerization where the sequence of
A's and B's is random,
-A-A-B-A-B-B-A-B-A-B-B-B-A-.
Block copolymer:
Built from first one polymer, and then another, as in
-A-A-A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-B-B-.

Graft copolymer:
Where a polymer of 'B' was grafted onto a polymer of 'A'.
-A-A-A-A-A-A-A-A-A-A-
|
B
|
B
|
Molecular Structure
• In each polymer molecule, the atoms are bound
together by covalent bonds. However, the separate
molecules, or segments of the same molecule, are
attracted to each other by weak “intermolecular
forces”, also termed “secondary” or “Van der Waals”
forces.
• In general, covalent bonds govern the thermal and
chemical stability of polymers.
On the other hand, secondary forces determine most
of the physical properties associate with specific
compounds.
Melting, dissolving, vaporizing, adsorption, diffusion,
deformation, and flow involve the making and breaking
of intermolecular bonds so that molecules can move
past one another or away from each other.
• Individual chains of polymers can also be
chemically linked by covalent bonds
(crosslinked) during polymerization or by
subsequent chemical or thermal treatment
during fabrication.
• Once formed, these crosslinked networks resist
heat softening, and solvent attack, but cannot be
thermally processed.

Linear Branched Cross-Linked Network

(more rigid)
Increase in Strength (in General)
e.g.,
• Linear Polymers: Polyethylene, poly(vinyl chloride)
(PVC), polystyrene, polymethyl methacrylate
(plexiglass), nylon, fluorocarbons (teflon).
• Branched Polymers: Many elastomers or rubbers.
• Cross-linked Polymers: Thermosetting polymers,
many elastomers or rubbers are also cross-linked
(vulcanized).
• Network Polymers: Epoxies, phenol-formaldehydes.
Tacticity (Stereoisomerism)

Atactic: An atactic polymer has chemical groups

attached to the polymer chain randomly on either side
of the carbon chain

Isotactic: An isotactic polymer has the chemical groups

attached to the same side of the carbon chain.

Syndiotactic: Syndiotactic polymers have the groups

alternately on opposite sides of the chain.
Tacticity affects the physical properties
• Atactic polymers will generally be amorphous, soft,
flexible materials
• Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible
Polypropylene (PP) is a good example
- Atactic PP is a low melting, gooey material
- Isotactic PP is high melting (176º), crystalline, tough
material that is industrially useful
- Syndiotactic PP has similar properties, but is very clear.
It is harder to synthesize
Classification of Polymers
Plastics – Greek word plastikos (Thermoplastics, Thermosets),
Elastomers
• The polymer chains can be free to slide past one another
(thermoplastic) or they can be connected to each other with
crosslinks (thermoset). Thermoplastics can be reformed and
recycled, while thermosets are not reworkable.
Thermoplastics
• Polymers that flow when heated; thus, easily reshaped and
recycled. This property is due to presence of long chains with
limited or no crosslinks. In a thermoplastic material the very
long chain-like molecules are held together by relatively weak
Van der Waals forces. When the material is heated the
intermolecular forces are weakened so that it becomes soft and
flexible and eventually, at high temperatures, it is a viscous
melt (it flows). When the material is allowed to cool it solidifies
again.
linear
branched

e.g. polyethylene (PE), polypropylene (PP), poly(vinyl chloride) (PVC), polystyrene

(PS), poly(ethylene terephthalate) (PET), nylon (polyamide), unvulcanized natural
rubber (polyisoprene)
Thermosets

Decompose when heated; thus, can not be reformed or

recycled. Presence of extensive crosslinks between long
chains induce decomposition upon heating and renders
thermosetting polymers brittle

crosslinked

e.g. epoxy, unsaturated polyesters, phenol-formaldehyde

resins, vulcanized rubber
Elastomers
• The polymer chains in elastomers are
above their glass transition at room
temperature, making them rubbery. Can
undergo extensive elastic deformation.
• Elastomeric polymer chains can be crosslinked, or
connected by covalent bonds. Crosslinking in elastomers
is called vulcanization, and is achieved by irreversible
chemical reaction, usually requiring high temperatures.

• Unvulcanized natural rubber (polyisoprene) is a

thermoplastic and in hot weather becomes soft and sticky
and in cold weather hard and brittle. It is poorly resistant
to wear. Sulfur compounds are added to form chains that
bond adjacent polymer backbone chains and crosslinks
them. The vulcanized rubber is a thermosetting polymer.
Crosslinking makes elastomers reversibly stretchable for
small deformations. When stretched, the polymer chains
become elongated and ordered along the deformation
direction. This is entropically unfavorable. When no
longer stretched, the chains randomize again. The
crosslinks guide the elastomer back to its original shape.

e.g., natural rubber (polyisoprene), polybutadiene (used

in shoe soles and golf balls), polyisobutylene (used in
automobile tires), butyl rubber (pond and landfill
linings), styrene butadiene rubber – SBR (used in
automobile tires) and silicone
 Polymers
• Made from small molecules (monomers)
which are linked together
– “mono” means one
– “mer” means unit
• The linked monomers form a chain-like
structure called a polymer
– “poly” means many
• The links are the covalent bonds between
the atoms
 Monomers Polymers
M

M M M

M
M M M
M

M M
Covalent
M Bonds
M

M Polymer
M

M
 Polymers

H
H
H
H C
H H
C H

H C H
C
C
H C C H
H

H
H Monomer
C H

Polymer
 Polymers
• Many millions of chains exist in the typical
polymeric part
• The chains are intertwined
– Like a mass of spaghetti
What determines physical, chemical
and mechanical properties of
materials?

• Molecular shape and movement

– Crystallinity
– Thermal transitions and crosslinks
– Aromaticity
– Pendant groups
– Chemical nature of the backbone
• Bonding between matrix and reinforcements
• Polarity (like attracts like)
 Polymers − Physical structure
• Amorphous − Polymers that have no regular
internal structure (just like the spaghetti)
• Semi-crystalline − Polymers that have some
internal structure (regular packing)
– Semi-crystalline polymers vary in the amount of
packing (crystallinity)
– Semi-crystalline polymers with high percentage of
packing are sometimes called crystalline
– No polymers are 100% crystalline
 Amorphous and Crystalline

Crystal
Regions

Amorphous Semi-Crystalline or Crystalline

(random entanglement) (regular packing)
 Polymers − melting, molecular
weight, crosslinking
• Polymers are classified into two groups
depending on whether they are crosslinked
– Thermoplastics (not crosslinked)
– Thermosets (crosslinked)
• Crosslinks are covalent bonds that link
between the polymer chains
• When crosslinking occurs, the polymers will no
longer melt
– When heated to a high temperature, they burn or char
 Thermoplastics
• Thermoplastics are not crosslinked and so they
will melt
• Thermoplastics are processed (molded) as
molten liquids
• Thermoplastics are cooled to solidify
• Thermoplastics can be re-melted repeatedly
• Kitchen example:

candy

• Examples of thermoplastics: polyethylene,

polystyrene, nylon, polycarbonate, acrylic,
Teflon®, PET (thermoplastic polyester)
 Thermosets
• Thermosets are crosslinked and do not melt
• Crosslinking is sometimes called curing
• Thermosets are processed as room
temperature liquids
• Thermosets are heated to solidify
• Kitchen example:

cake

• Examples of thermosets: polyesters, vinyl

esters, epoxies, phenolics, polyimides, silicones
 Thermal Transitions
• Heat Distortion Temperature (HDT)
• Glass transition temperature (Tg)
• Melting point (Tm)
• Decomposition temperature (Td)

Semi-crystalline
thermoplastic HDT Tg Tm Td

Hard, stiff Leathery Liquid Degraded

HDT Tg Td (Tm)
Thermoset

Hard, stiff Semi-rigid Degraded, Char

Temperature
The Great Dilemma in Polymers
• Polymers must have • Polymers must have
good properties good processing
– Good properties are – Good processing is
favored by high favored by low
molecular weight molecular weight
Mechanical Properties

Ease of Processing

Molecular Weight Molecular Weight

 The Great Dilemma In Polymers
• Thermoplastics meet the dilemma by
compromise
– High enough molecular weight to get adequate
properties
– Low enough molecular weight to process OK
• Thermosets meet the dilemma by
crosslinking
– Low molecular weight initially (for wetout and
processing) followed by curing to increase
molecular weight
– No compromise is required
 Polymers − Molecular shape
• Aromatic − Contains the benzene group
(sometimes called phenyl group)
– Named aromatic because it tends to have a strong
smell (like styrene)
– Increases stiffness
– Increases strength
– Increases non-flammability
• Aliphatic −Does not contain the benzene group
– Increases flexibility
– Increases toughness
– Increases weatherability
 ...C C C C...
...C ( C C )nC... C
C C
Polyethylene (no aromatic)
C C
C
C C C C
Polystyrene (pendant
C C C O C C C C C O C... aromatic)
O C C C C
Epoxy (aromatic backbone)
HO HO OH

O
....C C C C C...
C C C C C C C C C C C C
...C C C N C C C C... C C C C C C
C C C
C C H C C
C C C
Kevlar (aromatic backbone) HO C C C OH
C C C C C C C C
C C C C C C
....C C C C C...

Phenolic (aromatic network)

 Bonding
• Bonding is strongest when electrons are:
– Transferred (ceramics)
– Shared by many atoms (metals)
– Shared by two atoms (covalent)
• Weak bonding occurs without electrons
being transferred or shared
• These weak bonds depend upon polarity
 Polarity
N S S N

S N S N

O
d+
d- H H
d+
O
d- d+ d-
d+
C O C O ...C C O C...
d-
O
H H
Polyester is attacked by water molecules
Bonding in polymers by polarity
• Polar areas on the polymers attract other
polar areas on other molecules.
– Opposite charges attract
– The most electronegative atoms are those
that cause polarity
– The electronegative atoms are: F, O, N, Cl
– These are all in the upper right corner of the
periodic table
• Non-polar areas attract other non-polar
areas
 Bonding
OH OH Fiberglass − A highly polar molecule
d+
...O Si O Si O...
OH d-OH Sizing (alkylsilane) − Mixed polar/non-polar

CH3
d+
H3C Si O C C C C C C C...
CH3
Nonpolar regions (weak attraction)
d-
O
....C C O C C C C C...
d+

Polyester − Largely non-polar

Two types of composites are:
Fiber Reinforced Particle Reinforced
Composites Composites
 Properties of Composites
Dependent on:
• constituent phases
• relative amounts
• geometry of dispersed phase
– shape of particles
– particle size
– particle distribution
– particle orientation
 Composite Parameters
For a given matrix/dispersed phase system:
• Concentration
• Size
• Shape
• Distribution
• Orientation
 Parameters

Distribution Concentration Orientation

Shape Size