Topic 1 Introduction

Department of Materials Science and Metallurgy
Technology of Plastic
Materials
Topic 1 - Introduction and basic
concepts: thermoplastic materials
February 2018
Index
• Definition of polymer and plastic.
• Classification of polymers.
• According to their origin.
• According to their behaviour with temperature.
• Thermoplastics
• Thermosets
• Elastomers
• According to their consumption (industrial classification).
• According to their structure and molecular architecture.
• According to their chemical nature (families).
• Molecular weight.
• States of aggregation of polymers: amorphous/semi-crystalline. Crystallinity.
Technology of Plastic Materials Topic 1

What is a polymer?
• From the Greek:
Poly + mer = many parts
Material formed by long molecules, which in turn are formed
by the repetitive sequence of smaller molecules or groups of
atoms bonded by primary covalent bonds.
POLYMER = MACROMOLECULE
Plastics
Polymer + Additives
Elastomers

Repetitive unit
• The molecular structure of a polymer may be idealized as a
pearl necklace in which each pearl represents a repetitive
unit.

What is a plastic?
• Whatever material belonging to an extensive and
varied group formed wholly or partially by
combinations of carbon with oxygen, nitrogen,
hydrogen and/or other organic or inorganic
elements. These materials, though solid in their
final state, during certain stages of their processing
may be liquid and thus may be conformed using
different techniques, normally applying a
combination of heat and pressure. That is, plastics
are conformable materials constituted by
polymers.

Covalent bond:
Gas
Solid
ETHYLENE
(number of carbon atoms = 2) POLYETHYLENE
(> 10000 carbon atoms)
Gas
Liquid
BUTANE (4 carbon atoms)

OCTANE (8 carbon atoms)

Examples
--A-A-A-A-A-A-A--- -[A]n-
Polyethylene -[CH2]n-
Polyvinyl chloride -[CH2CH Cl]n-
Polystyrene
Styrene

The importance of secondary bonds

Due to the polarity of some functional groups, as for instance the amide group of
polyamides, it is possible the formation of hydrogen bonds (strong secondary bonds)
between chains (interchain bonding):
Amide group
+ Polyamide
Hydrogen bond
-
• Higher melting point (Tm)

Tm (PA66): 250-265 ºC
• Higher mechanical properties (stiffness and strength)
Hydrogen bonds between
• Problem: the material is sensible to water PA66 chains
Homopolymers and copolymers

• Homopolymer:
– Polymer that presents the same repetitive unit throughout its backbone.
• A-A-A-A-A-A-A-A-A-A-A-A- (homopolymer polyA)
• B-B-B-B-B-B-B-B-B-B-B-B-B- (homopolymer polyB)
H H H H H H
C C C C C C
H CH3 H CH3 H CH3

n
PP
• Copolymer:
– Polymer formed by two or more repetitive units in its molecular
structure.
H H H H
C C C C
H H H CH3
n m
Propylene-Ethylene copolymer Acrylonitrile-butadiene-styrene (ABS)
Types of copolymers
• Random copolymer
– A-A-A-B-A-A-B-B-B-A-B-B-A-
• Alternating copolymer
– A-B-A-B-A-B-A-B-A-B-
• Block copolymer
– A-A-A-A-A-A-B-B-B-B-B-
• Graft copolymer
-B-B-B-B-B-
-B-B-B-B-B-
-B-B-B-B-B-
A-A-A-A-A-A-A-A-A
Types of copolymers
• Random copolymer
– A-A-A-B-A-A-B-B-B-A-B-B-A-
• Alternating copolymer
– A-B-A-B-A-B-A-B-A-B-
• Block copolymer
– A-A-A-A-A-A-B-B-B-B-B-
• Graft copolymer
-B-B-B-B-B-
-B-B-B-B-B-
-B-B-B-B-B-
A-A-A-A-A-A-A-A-A
Classification of polymers
• According to their origin:
- Natural (natural rubber, silk, amber, wool, etc.)
- Synthetic
• According to their behaviour with temperature:
- Thermoplastics
- Thermosets
- Elastomers
• According to their consumption (industrial classification):
- High consumption plastics (commodities): > 75% of the total plastic consumption
- Technical plastics
- High performance plastics
• According to their structure and molecular architecture:
- Linear
- Ramified
- Crosslinked

Industrial classification of
plastic materials:
High performance plastics

(specialties)
Technical plastics
High consumption
plastics (commodities)
PVC
Amorphous Semi-crystalline
Classification of polymers according to

their behaviour with temperature
• Thermoplastics:
– They are polymers that when heated at certain temperatures are
converted into fluids, enabling their conformation to a desired
shape, which is preserved with cooling.
• Thermosets
– They are polymers that can not flow by increasing the temperature
for re-molding, as they thermally degrade. They are highly stiff
crosslinked polymers, being difficult to assign a repetitive unit.
• Elastomers
– They are formed by long macromolecules with a lot of free
movement (molecular flexibility), which enables their high
deformation with applying a relatively low stress and quick
recovering of their original shape with ceasing the applied stress
(elastic behaviour).


1. Thermoplastics
They have a structure that enables their reprocessing (mechanical recycling).
Temperature
Transformation process
Pressure
Thermoplastic Extrusion, injection, other processes Melted or softened

(normally it is found in a solid
state at room temperature)
material
Cooling
Homopolymers:
Polyethylene (PE)
Polypropylene (PP)
Polystyrene (PS)
Polyamide (PA)
Polycarbonate (PC)
Copolymers:
Acrylonitrile-butadiene-styrene (ABS)
Styrene-acrylonitrile (SAN)

2. Thermosets Transformation process/curing
(Temperature)
Thermoset resin Material in a solid state

(usually liquid at room temperature) (cured resin)
X
Heating
Heating of the cured material originates

its degradation
Thermoset
Epoxy resins (Three-dimensional network)
Unsaturated polyester resins
Phenolic resins
Peroxide
Unsaturated RO-OR
polyester
Styrene Double bond
Polyester backbone

3. Elastomers
The main characteristic of elastomers is their elastic-like mechanical behaviour, i.e., their
ability to deform significantly and elastically recover their deformation. They are also non-
crystalline, i.e., fully amorphous, materials.
Their faint crosslinking and chain

mobility enable them to recover
their initial state with removing
the applied stress.
Elastomer chains during application
of a certain stress
Elastomer chains in a Big non-linear elastic
relaxed state deformation even at low
applied stresses.
They are materials that are characterized by their
reduced strain-dependent elastic modulus, as their elastic
behaviour is non-linear.
• According to their structure and molecular
architecture:
• Linear
Ex.: HDPE, PP, Linear polyesters (PET, PBT, etc.)
• Ramified
Ex.: LDPE, HMS-PP
• Crosslinked
(thermosets, elastomers)
Ex.: crosslinked LDPE (XPE), cured epoxy resin,
vulcanized rubber
• According to their structure and molecular
architecture: HDPE
• Linear
Ex.: HDPE, PP, Linear polyesters (PET, PBT, etc.)
LDPE
• Ramified
Ex.: LDPE, HMS-PP
• Crosslinked
(thermosets, elastomers) XPE
Ex.: crosslinked LDPE (XPE), cured epoxy resin,
vulcanized rubber

• According to their chemical nature polymers
may be classified in families:
• Polyolefins (polyethylene - PE, polypropylene - PP)
• Acetals (polyoxymethylene - POM)
PE
• Acrylics (polymethylmethacrylate - PMMA)
• Cellulosic (cellulose acetate)
• Polyamides (Nylon®)
• Fluoroplastics (PTFE - Teflon©, Gore-Tex©) POM
• Polystyrenics (Polystyrene - PS, SAN, ABS)

PMMA
• Linear polyesters (Polyethylene terephthalate - PET, PBT, PEN)
• Polycarbonates
• Polyurethanes
• Etc.
Polyamide
PS PET

Molecular weight
During polymerization several different polymer macromolecules are formed, since
the monomers have the freedom to form independent chains.
As a consequence, polymerization is a statistical and random process. So, it is not

possible to assure that all formed molecules have the same molecular size. For that
reason, it is required to talk about average molecular weights.
Number of molecules (N)

Molecular weight
In the molecular weight distribution it is considered that the polymer is formed by
several fractions i containing Ni molecules (chains), each with a molecular weight Mi.
Two molecular weight concepts are commonly used:
___ ___
M n - Average numeric molecular weight M w - Average mass molecular weight
Arithmetic average of the molecular Mass average of the molecular weight

weight distribution distribution

Molecular weight
___
Mn =
∑N M = ∑N M = ∑x M
i i i i
___
M n = ∑ x i Mi
∑N N i
i i
___
M n - Average numeric molecular weight
M i - Average molecular weight (intermedium) corresponding to interval i
x i - Fraction of the total number of chains inside interval i
___
Mw =
∑ M N i
2
i
= ∑w M
___
M w = ∑ w i Mi
∑M N i i
i i
Ni Mi
wi =
___
∑ Ni Mi
M w - Average mass molecular weight
M i - Average molecular weight (intermedium) corresponding to interval i
w i - Mass fraction of chains inside interval i

Molecular weight
___
• M n is controlled by the smaller molecules (lower weight), which dominate in quantity.
___
• M w is defined by the molecules with a higher specific weight, which tend to be lower in
number than the smaller ones since their distribution is displaced in the direction of lower
molecular weights.
• When the molecular weight is extremely high, a third molecular weight parameter is often used
___
( M z ).
Number of molecules (N)

___
Mz =
∑ i i
N M 3
∑N M i i
2

Molecular weight
One way of measuring the amplitude of the molecular weight distribution
___ considers the so-
___
called dispersity index (DI), which is defined as the quotient between M w and M n :
___
Mw
DI = ___ DI ≥ 1
Mn
• The dispersity index is very different from a polymer obtained by free radical polymerization
(higher DI’s) than a polymer obtained by anionic or cationic polymerization.
• When DI = 1 it is said that the polymer is monodisperse.

Molecular weight
An alternative way of expressing the average molecular size of a polymer is through the
polymerization degree (n), which represents the average number of monomer units in a given
chain:
___ ___
nn - Average numerical polymerization degree
Mn Mw
nn = ___
nw = ___ nw - Average weight polymerization degree
___
m m m - Molecular weight of the monomer
__
In a copolymer with two or more different monomers, m is calculated as:
___ fj - Chain fraction

m = ∑ f jm j
mj - Molecular weight of the monomer j

Molecular weight
• Influence of the molecular weight on the material’s properties
Molecular weight
Influence of crystallinity and molecular weight on

the physical characteristics of PE
Source: R. B. Richards, Polyethylene-Structure, Crystallinity
and Properties, J. Appl. Chem.. 1, 370, 1951.

Molecular weight
Effect of the dispersity index (DI) on

the viscosity and flexural strength of
a polystyrene.
Topic 1
States of aggregation of polymers

Spaghetti-like
Amorphous
Semi-crystalline
Each pearl represents one

repetitive unit formed from one or
more monomers
Amorphous Semi-crystalline
Tm
(melting)
Rubber- The aggregation state and
like
TEMPERATURE
the temperature determine

TEMPERATURE
Viscous Viscous
liquid Rubber-like liquid Flexible solid
the final behaviour of the
Tg (glass Tg (glass system
Vitreous transition) Vitreous state transition)
state (brittle)
MOLECULAR WEIGHT MOLECULAR WEIGHT
• Amorphous polymers
– Description
– Glass transition temperature (Tg)
• Semi-crystalline polymers
– Description
– Glass transition temperature (Tg)
– Melting temperature (Tm)

– Random disposition
(like in a spaghetti plate)
– Partially ordered
(they present amorphous and
semi-crystalline phases)


Main characteristics of an amorphous polymer:
– An amorphous polymer may be considered as a
“frozen liquid polymer”.
• Molecules do not have a spatial order.
• Molecules are random-distributed by interpenetrating each

other.
• Polymer chains present an almost null molecular mobility,

which starts increasing above the glass transition temperature
(Tg).


• Amorphous polymers Amorphous
Glass transition temperature

(Tg):
If an amorphous polymer is
heated it will arrive to a point
where the chain segments start
to gain molecular mobility. M2
This point marks the so-called
glass transition temperature Vitreous solid - rubbery solid transition (glass
(Tg). transition temperature, Tg).
Rubbery solid - viscous liquid transition (softening
temperature).
The concept of melting temperature (Tm) only applies to semi-crystalline polymers.


Glass transition temperature (Tg):
Temperature below which the molecular mobility of the polymer chains
is very restricted and basically limited to the vibrations of covalent bonds.
When the Tg is reached, chain segments of 50-100 atoms start to gain

molecular mobility.
Above the Tg, there is mobility of big chain segments (> 100 atoms),
enabling them to slide past one another (creep).


Influence of the Tg in the behaviour of the polymer:
Above the Tg:
- Loss in mechanical properties (stiffness)
- Associated specific heat (ΔCp)
- Expansion coefficient
Vitreous transition obtained by
differential scanning calorimetry (DSC)
The Tg of a polymer depends on its chemical nature and on other

physical factors, such as the aggregation state, presence of plasticizers, etc.


Factors affecting the Tg:
• Chemical nature (chain structure)
Flexibility Tg
• Molecular weight
___
Mn Tg
• Molecular architecture
Ramifications Tg
Crosslinking Tg
• Plasticizers Tg

• Copolymers
• Random and alternating copolymers: one single Tg
Random copolymer:
1 w w
= A+ B
Tgco TgA TgB
Alternating copolymer:
Tgco = TgA wA + TgB wB
• Block and graft copolymers: 2 different Tg
Block copolymer: Graft copolymer:


• Elastomers
• Extremely low Tg (clearly below room temperature)
• Slightly crosslinked polymers
Example of elastomer vulcanization:
Elastomer chains in a
relaxed state
Elastomer chains during the

application of a certain stress

- The polymer chains may present an ordered
structure which consists in their self-folding.
- The ordered part is crystalline, i.e., it has a
spatial order, coexisting with an amorphous
phase.
- These structures are thermodynamically
favoured.
Besides self-folding, the chains may pile up.

A pile up of self-folding polymer chains is
called lamella.

There are three basic orders of polymer crystalline ordering:
- Initial chain self-folding.
- Pile up of the self-folding chains to form fibrillar lamellas.
- Growing and order of the lamellas around a crystalline core to form the
so-called spherulites.
Chain self-folding Pile up (lamella) Spherulite


Conditions for polymer crystallization:
Both the molecular architecture as well as chain configuration affect the possibility
of polymer crystallization.
Crystallization is hampered in polymers with complex repetitive units or complex
functional groups.
H H H H
C C C C
H n H H n
Polyethylene (PE) PE’s orthorhombic crystal
Polystyrene (PS)
The big volume of the phenyl On the contrary, due to the
group makes that under common small volume of its
processing conditions PS does functional groups, PE tends
not crystallize (amorphous). to crystallize. Orthorhombic crystal

Conditions for polymer crystallization:
• Linear polymers:
- They crystallize more easily (less restrictions to chain alignment, as for instance occurs in the
case of the presence of ramifications or crosslinking).
- However, depending on their tacticity (stereoisomery), they may be amorphous (atactic) or
semi-crystalline under typical crystallization conditions (isotactic and syndiotactic).
• Copolymers:
- The more irregular and random is the disposition of the repetitive unit, the less tendency they
will have to crystallize.
- Due to this, normally random and graft copolymers are amorphous, while both alternating and
block copolymers may typically develop a certain degree of crystallinity.


Amorphous Tie molecules

region Crystalline core
Fibrous lamellas
Polymer spherulite

Structural regularity:
a) Symmetry: the presence of asymmetric carbons in the polymer backbone may
give way to three different structures, depending on the spatial disposition of the
functional group: atactic, isotactic and syndiotactic.
Among them, the isotactic one is the one that shows the highest symmetry and
tends to lead to a more crystalline polymer.
b) Flexibility of the main chain: a lower chain flexibility increases the tendency to
crystallize, since the restriction to the number of possible conformational changes
facilitates the formation of preferential conformations required for ordered
packing.
c) Tacticity: isotactic and syndiotactic polymers have structural regularity and tend
to be crystalline, while atactic polymers are amorphous.
C – asymmetric carbon
Isotactic
R=…
Syndiotactic -CH3 – Polypropylene (PP)
– Polystyrene (PS)
Atactic
-CN – Polyacrilonitrile (PAN)

d) Cis and trans configurations: there are two types of natural rubber coming from
isoprene. There are two possible configurations:
Hule
Gutta-percha
Isoprene
Hule: Gutta-percha:
Cis configuration Trans configuration
Its characterized by its flexibility and Due to its high structural regularity its
elasticity (irregular structure that inhibits crystalline and thus less elastic than hule (for
crystallization). instance it is used in the coating of golf balls).

e) Ramifications: the most clear example on the effect of ramifications on the

crystallinity degree of a polymer is polyethylene:
HDPE (linear) LDPE (ramified) LLDPE (short-chain branching)
Properties HDPE LLDPE LDPE
Density (kg/m3) 952-965 918-940 917-932
Melting temperature, Tm (ºC) 130-137 122-124 98-115
Stress at break (MPa) 22-31 13-28 8.3-31
Maximum strain at break (%) 10-1200 100-965 100-650
Elastic modulus (MPa) 1070-1090 260-520 170-280


f) Copolymers: only regular copolymers may crystallize (alternating and block

copolymers).
Alternating copolymer: Block copolymer:
Non-crystallizable:
Random copolymers: Graft copolymers:


Crystallization from the melt (crystallinity degree):
The crystallinity degree (Xc) of a polymer depends on the cooling rate during solidification as
well as on the chain configuration, since polymer chains must pass from a disordered state in the
melt (amorphous) to a partially-ordered one, which requires time for their movement and alignment.
• It can be estimated using different methods:
- Density: it assumes that there is a higher than 20% difference between the density of the
amorphous phase and that of the crystalline one. It enables to determine both the weight as well
as volumetric crystalline fractions.
Volumetric crystallinity Weight crystallinity
ρ − ρa ρc ⎛ ρ − ρa ⎞
φc = χc ( % ) = ⎜ ⎟ × 100
ρc − ρa ρ ⎝ ρc − ρa ⎠
ρ – Polymer density ρc – Calculated from the crystalline unit cell
ρa – Density of the amorphous phase ρa – Extrapolated from the melt
ρc – Density of the crystalline phase
- Differential scanning calorimetry (DSC)
- Spectroscopy (X-ray diffraction, XRD; Raman microscopy)

Crystallization from the melt (crystallinity degree):
Crystallization implies a reduction in specific volume
and thus an increment in density due to packing.
• It can be estimated using different methods:
- Density
- Differential scanning calorimetry (DSC)
- Spectroscopy (X-ray diffraction, XRD; Raman
microscopy)
Changes in specific volume for amorphous,

crystalline and semi-crystalline polymers
Amorphous halo
XRD spectrum of a PE
Differential scanning calorimetry (DSC)

Sample Reference Oven with Reference
sample oven
Heat flux DSC Power compensation DSC

- One single oven - Separated ovens
- Temperature difference - Electric power difference
- Design used by Mettler-Toledo - Design used by Perkin-Elmer

Differential scanning calorimetry (DSC)

Thermograms: semi-crystalline material - heating
- Analysis of the glass transition

temperature, Tg (amorphous phase)
- Analysis of the melting

temperature, Tm (crystalline phase)
Technology of Plastic Materials

Melting temperature (Tm)
• It is the temperature at which polymer chains have

such mobility that they abandon the lamellar
order.
• The Tm depends on the thermal history and
lamellar thickness.
• Tm is higher than the Tg.

Influence of the Tm in the behaviour of the

polymer
• The Tm marks an important change in the
properties of the polymer:
– Loss in rigidity (amorphous fluid)
– Transition with energy absorbance (endothermic)
• The Tm of a polymer depends on its chemical

nature and molecular weight as well as on the
thermal history.

Influence of the Tm in the behaviour of the

polymer
Repetitive unit Repetitive unit Funct. group

Factors affecting the Tm

• Depends on the molecular weight and ramification
degree:
- A high proportion of chain ends, either low weight chains or
ramifications, introduces defects in the crystal, reducing the Tm.
• Depends on the structure of the chain:

- Higher chain flexibility Tm
- Secondary intermolecular bonds (hydrogen bonds) Tm
- Stiffening functional groups Tm
- Large and flexible functional groups Tm

Relations between structure and properties

POLÍMERO SEMICRISTALINO
Amorphous polymer
POLÍMERO AMORFO Semi-crystalline polymer
Degradación
Thermal térmica
degradation
Degradación térmica
Thermal degradation
Tm (melting)
Viscous liquid Viscous liquid Rubber-like
TEMPERATURE
TEMPERATURE
Rubber-like
Flexible solid
Tg (glass transition) Tg (glass transition)
Vitreous state Vitreous state (brittle)
MOLECULAR WEIGHT MOLECULAR WEIGHT

Topic 1 Introduction

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Department of Materials Science and Metallurgy

Technology of Plastic Materials Topic 1

Technology of Plastic Materials Topic 1

Technology of Plastic Materials Topic 1

Technology of Plastic Materials Topic 1

BUTANE (4 carbon atoms)

Technology of Plastic Materials Topic 1

Technology of Plastic Materials Topic 1

The importance of secondary bonds

• Higher melting point (Tm)

Homopolymers and copolymers

H CH3 H CH3 H CH3

Technology of Plastic Materials Topic 1

High performance plastics

Classification of polymers according to

Technology of Plastic Materials Topic 1

Classification of polymers according to

Thermoplastic Extrusion, injection, other processes Melted or softened

Classification of polymers according to

Thermoset resin Material in a solid state

Heating of the cured material originates

Classification of polymers according to

Their faint crosslinking and chain

Technology of Plastic Materials Topic 1

• Polystyrenics (Polystyrene - PS, SAN, ABS)

Technology of Plastic Materials Topic 1

As a consequence, polymerization is a statistical and random process. So, it is not

Technology of Plastic Materials Topic 1

Two molecular weight concepts are commonly used:

Arithmetic average of the molecular Mass average of the molecular weight

Technology of Plastic Materials Topic 1

Technology of Plastic Materials Topic 1

Number of molecules (N)

Technology of Plastic Materials Topic 1

• When DI = 1 it is said that the polymer is monodisperse.

Technology of Plastic Materials Topic 1

___ fj - Chain fraction

Technology of Plastic Materials Topic 1

Influence of crystallinity and molecular weight on

Technology of Plastic Materials Topic 1

Effect of the dispersity index (DI) on

States of aggregation of polymers

Each pearl represents one

the temperature determine

States of aggregation of polymers

Technology of Plastic Materials Topic 1

States of aggregation of polymers

Technology of Plastic Materials Topic 1

States of aggregation of polymers

• Molecules are random-distributed by interpenetrating each

• Polymer chains present an almost null molecular mobility,

Technology of Plastic Materials Topic 1

States of aggregation of polymers

Glass transition temperature

The concept of melting temperature (Tm) only applies to semi-crystalline polymers.

States of aggregation of polymers

When the Tg is reached, chain segments of 50-100 atoms start to gain

Technology of Plastic Materials Topic 1

States of aggregation of polymers

The Tg of a polymer depends on its chemical nature and on other

Technology of Plastic Materials Topic 1

States of aggregation of polymers

States of aggregation of polymers

Tgco = TgA wA + TgB wB