Section 12:

POLYMERS and COMPOSITES

 Polymers – basic concepts
Terminology:
• Polymer – “Poly” meaning “many” and “mer” meaning “unit”.
• Monomers – Basic building blocks of a polymer.
• Macromolecule – extremely large collections of molecules to form one
polymeric chain .
• Plastics – a synonym for polymers.

• The word “plastic” comes from the Greek word “plastikos”, meaning
capable of being molded and shaped.
• Polymers can be natural or synthetic (man-made)
• The earliest polymers, such as cellulose, were made from natural organic
materials from animals and vegetable products

Most commonly, polymers are constituted by a hydrocarbon backbone

(chains formed by C and H) to which different functional groups may be
inserted. However, other structures exist, too; for example, silicon (Si) can
form polysiloxanes (silicones), based on –Si-O-Si-O-Si- chains; they are
widely used as sealants.
Advantages of using polymers:

• low cost
• low electrical and thermal conductivity (insulation)
• low density
• high strength-to-weight ratio secon
dary
• resistance to chemical corrosion bond
ing
• noise reduction
• assortment of colors (aesthetics)
• ease of manufacturing
• minimal additional surface treatments
• forms of availability such as: tubes, films, sheets, plates, rods, etc.

Additives can be used:
fillers, lubricants, pigments…
Ex.: carbon black (in tires)
Limitations
• Low mechanical properties
• Low thermal resistance
• Flammability
• Damage due to visible light and UV
 Polymerization
Polymerization is the process of combining many monomers into a
covalently bonded chain or network.
ADDITION POLYMERS
All the monomers from which addition polymers are made are alkenes or
functionally substituted alkenes (alkenes have at least one C=C bond).
Example: polyethylene, derived from the ethylene (H2C=CH2).
Many of poly-addition reactions are known to proceed in a stepwise fashion by
way of reactive intermediates. A general diagram illustrating this assembly of
linear macromolecules (chain growth polymers) is shown below.
Note that an initiating species, i.e. a catalyst (indicated as Z*), is necessary so
that the reaction can run.
CONDENSED POLYMERS
In polycondensation, polymerization proceeds by functional group
transformations; it typically involves the loss of a small by-product, such
as water, and combines two different monomers in an alternating
structure. Example: polyethylenterephtalate (PET):
terephthalic acid Ethylen glycol

Condensation polymers form more slowly than addition polymers, and often
the reaction requires heat. The terminal functional groups on a chain remain
active, so that groups of shorter chains combine into longer chains in the late
stages of polymerization. The presence of polar functional groups on the
chains often enhances chain-chain attractions, particularly if these involve
hydrogen bonding; thus, crystallinity and tensile strength are increased.
 Molecular weight
• Molecular Weight Distribution (MWD), is the sum of the molecular weights
of the mers in a macromolecule (polymer chain)

• Degree of Polymerization (DP) is the size (length) of the polymer chain

MWD and DP strongly affect the

mechanical properties and viscosity of
polymers
Composition
 Structure

THERMOPLASTICS
• Linear Polymers
Sequential structures
• Branched Polymers
Increased resistance to
deformation and applied loads.

• Cross-Linked Polymers
higher hardness, strength,
stiffness, brittleness, and better
dimensional stability.

THERMOSETS
• Networked Polymers
(highly cross-linked), have a higher
resistance when exposed to high
energy radiation, UV light, X-rays, or
electron beams, as well as higher
mechanical properties.
• Copolymers contain two types of monomers
Ex: Styrene-butadiene, used in making tires

• Terpolymers contains three types of monomers

Ex: Acrylonitrile-butadiene-styrene, used to make helmets

Purposes:
- Take the «best» from the constituting polymers
- Modulation of properties
 Crystallinity
Polymers can be:

• Amorphous, the polymer chains exist without order (e.g. PVC).

• Semi-crystalline crystallites: the regions arrange themselves in an

orderly manner. PTFE can reach 98% crystallinity

Crystallinity can be increased by controlling (decreasing) the rate of

solidification during the cooling process
 Types of polymers
THERMOPLASTICS

Polymers that can undergo shaping upon heating, return to their original
state and be reformed indefinitely
They are recyclable.

Ex: Acrylics, Nylons, Polyethylenes

THERMOSETS

When long chain molecules in a polymer become one giant molecule with
strong covalent bonds (cross-links) the polymer is permanently set.

These polymers can be formed only the first time; ex: resins, adhesives

The curing reaction of a thermoset is irreversible (unlike thermoplastics)

No Tg value
ELASTOMERS

Linear polymers in which a low number of bridging bonds are introduced,

which give the material a three-dimensional structure and ensure very high
elastic properties (up to 800-1000% ONLY ELASTIC deformation). These
bonds (typically sulphur-based bonds) are introduced after the molding of
the material, through a chemical reaction.
Effect of glass transition temperature (Tg)

A = thermosets or
thermoplastics below Tg

B = thermoplastics above Tg
C = elastomer
The tensile stress-strain curve (A) for semicrystalline polymers at T > Tg:
Upper and lower yield points of the curve are followed by a near horizontal
region.
Upper yield point: a small neck forms within the gauge section.
Within this neck the chains become oriented, which leads to localized
strengthening. There is a resistance to continued deformation at this point
and specimen elongation proceeds by the propagating of this necking region
along the gauge length.

At T < Tg (rigid polymer); curve (B) Curve (B)

Curve (A)
Effect of environmental temperature
 Processing of polymeric materials

Processing technologies of Processing technologies of

thermoplastic materials: thermosetting materials:

• Molding, injection • Injection molding + transfer

(for polymer-matrix
• Thermoforming composites)

• Extrusion • Compression

• Blowing (injection of gas bubbles) • Pultrusion (for polymer-matrix

composites)
• Calendaring (rolling)
• Rotational molding
PULTRUSION

- Similar to extrusion of metallic parts

- Pultrusion involves pulling resin-impregnated glass strands through a die
- Standard extruded shapes can easily be produced such as pipes, channels,
I-beams, etc.
RESIN TRANSFER MOLDING

- Resin transfer molding is a manufacturing method that is quite similar to

injection molding where plastic is injected into a closed mold

- In the RTM process the preform (precut piece(s) of reinforcement) is placed

in the mold, the mold is closed and the thermoset plastic matrix is injected into
the mold, once the matrix is cured the part is ejected
 Polycarbonate shelter

- Polycarbonate produced by
thermoforming
- Fixed with an aluminum frame
(PC reacts with glues and
cannot be laid by gluing)
- Transparency
- Possibility of being colored
- Possibility of cold bending
- Scratch resistant
- UV-protection coating on the
external side via PVD
(sputtering)
- Additives for UV protection
 Polyethylene tubes and conduits
- Good corrosion resistance
- Resistance to chemicals and bacteria
- Non-toxic
- Resistance to atmospheric agents and UV
radiation (added with carbon black)
- Resistance to attack by insects and rodents
- Good abrasion resistance (HDPE)
- Toughness
- Smooth surfaces (resistance to incrustations and
reduced pressure drops)
- Flexibility
- Low costs
- It does not develop toxic or corrosive gases
following combustion

Applications
- Drinking water transport
- Irrigation systems
- Sewers
21
- Pipeline
 Thermal coat

Expanded polystyrene
(EPS)
k = 0.035-0.046 W/mK
Good thermal insulation
White color
It can be added with
graphite (gray/black) to
improve thermal insulation
Closed cell polyurethane foam
k = 0.020-0.035 W/mK
Very good thermal insulation.
The cells can contain air or more
insulating gas. Suitable for
severe climatic/environmental
conditions
External coatings of the thermal coat:
- Acrylics
- Siloxane
- Acrilsiloxanes

Functions:
- Moisture barrier (water penetration and coat
degradation, loss of insulating function)
- Plaster protection
- Mechanical protection and UV barrier

Requirements:
- Good adhesion to the substrate (use of primer)
- No abrupt variations in elasticity
# layers of plaster with decreasing
flexibility
# use of a polymeric mesh that
accompanies the movements of the
substrate and prevents the coalescence of
the cracks in the final state of the plaster
 Seismic elastomeric base isolators

Use in earthquake engineering

They consist of alternate layers of steel and elastomer sheets, and may have
a lead core inside.
They are characterized by reduced horizontal stiffness and high vertical
stiffness, in order to reduce the lowering of the structure under load.
The lead core has the purpose of limiting elastic displacements and further
improving the dissipative capacity of the structure.
They are relatively expensive.
 RUBBER ISOLATORS

Use of a passive structural vibration control technology preservation of

building structure’s integrity
 Composites

A composite material is a combination of two or more chemically distinct

and insoluble phases with recognizable interface, in such manner that its
properties and structural performance are superior to those of the
constituents acting independently.

Generally, one material forms a continuous matrix while the other provides
the reinforcement.

Composites can be classified by their matrix material which include:

- Metal-matrix composites (MMCs)

- Ceramic-matrix composites (CMCs)

- Polymer-matrix composites (PMCs), which are sometimes referred to

as organic matrix composites (OMCs)
MMCs - Metal Matrix Composites
- The matrix is relatively soft and flexible.
- The reinforcement must have high strength and stiffness
- Since the load must be transferred from the matrix to the reinforcement, the
reinforcement-matrix bond must be strong.
MMCs use:
-Two types of particulates (dispersion strengthened alloys and regular
particulate composites)
- Or long fiber reinforcements

PMCs - Polymer Matrix Composites

- The matrix is relatively soft and flexible
- The reinforcement must have high strength and stiffness
- Since the load must be transferred from matrix to reinforcement, the
reinforcement-matrix bond must be strong

CMCs – Ceramic Matrix Composites

- The matrix is relatively hard and brittle
- The reinforcement have high mech. properties to stop crack propagation
- The reinforcement must be free to pull out as a crack grows (energy
dissipation), so the reinforcement-matrix bond must be relatively weak
Reinforcement mechanisms due to fibres

Load trasfer

Debonding (pull-out)
 Reinforcement mechanisms due to particles

CRACK DEVIATION

CRACK BLOCKING

Energy
INCREMENT OF consumption
CRACK PATH

PARTICLE
BREAKING
 Rule of mixtures
The rule of mixtures predicts some properties of the composite (e.g. density,
elastic modulus, electrical conductivity, thermal conductivity) knowing
the properties and volume fractions (f) of matrix and reinforcement.
ρc = f m ρm + f f ρ f Note that f m = 1 − f f
where the subscripts m and f refer to the matrix and fiber, respectively.

The rule of mixtures can also be used to predict the modulus of elasticity
when the fibers are continuous and unidirectional.

Parallel to the fibers, the modulus of elasticity may be as high as:

Ec = f m E m + f f E f
Perpendicular to the fibers, the modulus of elasticity may be as high as:
1 ff fm
= +
Ec E f Em
 Fiber-reinforced composites
- Fiber reinforced composites provide improved strength, fatigue resistance,
Young’s modulus and strength to weight ratio over the constituent materials.
- This is achieved by incorporating strong, stiff, yet brittle fibers into a more
ductile matrix.
- Generally speaking the fiber supplies the strength and stiffness while the
matrix binds the fibers together and provides a mean of transferring the load
between fibers
- The matrix also provides protection for the fibers
Some commonly-used fibers for polymer
matrix composites:
- Glass fibers
- Carbon fibers
- Aramid fibers (ARomatic polyAMIDes,
e.g. Kevlar)

Some commonly-used fibers for metal

matrix composites:
- Boron fibers
- Carbon fibers
- Oxide ceramic and non-oxide ceramic
fibers
Structure created in 1990 for the Italia 90 FIFA World Cup.

It comprises two "sails", with a total surface area of 4800 m2, having
negative curvature surfaces (saddle).

The structure is a
“membrane” with PTFE
matrix and glass fibers as
reinforcing elements