Chemistry Plastics

1
Origin, Construction, Structure

and
Physical Behaviour of Plastics, State Diagrams
Atom-Model
Shells
Core
Neutron Proton
Electron
X:Hdbuch\Werkstoffe\
Einfuehrung\1_1_2.ppt
2
Composition of Plastics
Element Atom
Smallest
Module
Chemical Compound Molecule
Basic Elements
carbon C 4 - valent
hydrogen H 1 - valent
oxygen O 2 - valent
nitrogen N 3 - valent
chlorine CL 1 - valent
3
From Crude Oil crude oil

to Plastics 100 %
diesel and heating oil other oils

70 % 10 %
benzines
20 %
fuels 13%
chemical rowmaterials
7%
chemical products
3%
plastics
4%
PVC PE/PP PU/PS PA/UP
Destillation of fractionating tower
Crude Oil gases

petroleum ether
heavy petrol (naphtha)
petroleum
gasoil
square-type expansion piece
petroleum vapour
Öl + water vapour
pipe oven
about 400 °C
4
Cracking from Benzine to Monomers
benzine butylene
styrene
butane
+ benzol
ethylene
+ chloride
ethane
vinyl chloride
vapour 850 °C
propylene
cracking oven
Cracking Process
octane
molecule
1st phase
cracking of the chain
2nd phase
formation of small
molecules
ethylene ethane
5
polymerisation
monomer + + +
ethylene
splitting of the + + +
double bonding
polymer
polyethylene
Co - Polymers
Polymer 1
e. g. PS
Polymer 2
e. g. Acrylnitril
Co - Polymer
e. g. SAN
6
Polyblends
plastic 1 plastic 2 plastic 3
+ =
Polycondensation
Diamin Disäure
H2 O
Polyamid
7
Polyaddition
+ +
Isocyanat Polyol
Polyurethan
The Field of Plastics
Synthetic Plastics Modified Natural Materials
Polymerisates Polycondensates Polyadducts

Celluloseacetat
Thermoplastics Thermoplastics Thermoplastics
Cellulosepropionat
Polyethylen Polyamide lineare
Polyurethane
Polypropylen Polycarbonate
Thermosettings
Polyvinylchlorid Polyethersulfon
Elastomeres Elastomeres Epoxidharz
vernetzte
Nitrilkautschuk Silikonkautschuk
Polyurethane
Styrol-Butadien- Thermosettings
kautschuk
Phenolharz
ung. Polyester
8
Secondary Valency Forces
Polymer
Chain
Amorphous Thermoplastic
Examples:
PS
PVC
PMMA
PC
9
Semicrystalline Thermoplastic
Examples:
PE
PP
PA
PET
PBT
POM
Difference between: amorphous - semicrystalline
Property amorphous semicrystalline

molecular structure disordered linear
appearance,colour crystal clear opaque
mech. behaviour brittle tough, elastic
shrinkage low (0,3- 0,7 %) high (1,5 - 3 %)
chem. resistance low good – very good
abrasion, wear high low
anti-friction (or lubricating) properties bad good
softening range big (about 200) small (about 1- 20)
10
Shrinkage Values of some Thermoplastics

[%]
4
3,5
2,5
1,5
0,5
0
PA POM PE PP PBT PC PS ABS
Thermosetting,close-mesh crosslinked
11
Elastomer, wide-mesh crosslinked
Distribution of Polymerchain Length

of two Polymers with the same
Average Level of Polymerisation
Fractions
of the
Polymer
Polymerkettenlängen
Chain
Length
Anteile der
Kettenlänge
Chain Length
12
Distribution of the Polymer Chain Lengths

at different Charges
Charge 1
Number
Charge 2
Charge 3
Chain Length
Size of the Macromolecules

The length of the macromolecules is about 1/1.000.000 to
1/1.000 of a millimeter.
The thickness of a macromolecule is about (2 or 3)/10.000.000 millimeters.
If we consider in thougt as a theoretical experiment that a molecule

would increase to a thickness of 1 cm, than it could have a length
up to 50 m.
It is spoken from macromolecules, if more than 1000 single molecules

(=monomers) are bonded together.
13
Impact of the increasing Length of the

Molecules on several Properties
Together with elongation of the molecule

chain length, following properties will be
changed:
• higher strength (Festigkeit)
• higher toughness (Zähigkeit)
• higher chemical resistance
• worse flow characteristics
Dependency of the Properties

from the Chain Length
no longer processable
Injection moulding
upper limit
extrusion
sum of the good properties
lower limit
chain length
14
Forces within the Material
innermoleculare bonding forces

(chemical bonding forces)
intermoleculare bonding forces
(physical bonding forces)
State Diagram of
Amorphous Thermoplastics
ET FT ZT
solid thermoelastic thermoplastic
Tensile strength
elongation
at break
ultimate
ET = softening point range temperature

FT = flow temperature range
ZT = decomposition temperature range
15
State Diagram of Semicrystallite Thermoplastics
ET KT ZT
hard-brittle hard-tough to thermoelastic thermoplastic
Tensile strength
elongation
at break
ultimate
temperature
ET = softening point range
KT = Crystalline melt temperature range
State Diagram Thermosettings
hard-brittle ZT
Tensile strength
elongation
at break
ultimate
temperature
16
State Diagram of Elastomeres
ET ZT
hard-toughelastic rubberelastic
Tensile strength
elongation
at break
ultimate
temperature
ET = softening point range
State Diagrams of several Thermoplastics
PVC - U ET FT ZT
PVC - P ET FT ZT
PMMA ET FT ZT
PC ET FT ZT
ABS ET FT ZT
PE - HD ET KT ZT
PP ET KT ZT
PVDF ET KT ZT
-100 - 50 0 50 100 150 200 250 300 350 400

Temperature in °C
z. brittleness hard - hardelastic elastic -
plastic
17
General Properties of Plastics (1)
to the good properties belong:

– low weight at good mechanical properties
– good electrical isolation property
– excellent resistance against chemicals and weathering
influences
– little heat conductivity
General Properties of Plastics (2)
on the other hand there are:

– a bad heat resistance
– a big thermal expansion
– a small elastic-modulus (E-module)
– the time dependency of the mechanical
properties
18
Mechanical Properties -
at Plastics everything is different
• niveau of the properties
• temperature dependency
• Creeping and flow
• nonlinearities (influence of the impact)
• ageing
Damage of Plastics
The molecule chains, additives and colours are

partial very sensitive and can be damaged.
Reasons Effects
• high mass temperature • strength of the parts

• long residence time will decrease
• high injection speed • colours will be darker
• high pressure back flow • additives will gas out
• high srew speed
19
Moisture Absorption
Reasons Failures, Problems
• moisture streaks
• storage of the granulate
• brittle fracture
• maintenance of the dryers • Higher waste at vanishing and
• material hopper too big, galvanization
not covered
• feed temperature too low difficult plastics:
• decompression too big or

----------------------------------
too fast
Drying of the Material

Dryer
• drying cabinet
• recirculating air dryer
• dry air dryer
• nitrogen dryer
Test Methods
• judging of the melt
• weighing IR-drying
• carbid-method
• Karl-Fischer-titration
20
Nützliche Infos aus Datenblättern

der Rohstoffhersteller
Temperatur δ °C Drücke bar

δ Einzug Spritzdruck
δ Zylinder Nachdruck
δ Masse Staudruck
δ Werkzeug Geschwindigkeit m/s
bzw.
U/min
δ Trockner und Schneckenum-
Zeit fangsgeschwindig-
keit
Zusätzliche Informationsquelle: Campus® Datenbank
Kunststoffbezeichnungen (1)
Kunststoffe werden durch ihren chemischen Namen

und durch ihr Kurzzeichen bezeichnet.
Beispiel:
Polyoximethylen/Polyacetal POM
(chemischer Name) (Kurzzeichen)
21
Kunststoffe erhalten von den Herstellerfirmen indivi-
duelle Handelsnamen.
Beispiel:
Ultraform POM der Firma BASF
Hostaform POM der Firma Ticona
Delrin POM der Firma Du Pont
Jeder Hersteller stellt von einer Werkstoffart z. B. POM unter-

schiedliche Typen her und hängt an die Handelsnamen noch
zusätzliche Bezeichnungen an.
Beispiel:
Ultraform W 2210
Ultraform Handelsname der Firma BASF für POM

W Buchstabe kennzeichnet die Fließfähigkeit
Zahlen geben Aufschluss über die Eigenschaften
(z. B. Zähigkeit, Zuschlagstoffe, ...)
Jeder Hersteller hat seine eigenen Bezeichnungen.
22
Wirkprinzipien bei Füllstoffen
• Verbesserung der mechanischen Kennwerte

• Erhöhung der Wärmeformbeständigkeit
• geringe Schwindung
• Verbesserung des Kriechverhaltens auch bei
erhöhter Temperatur
• Anderes Fließ- und Erstarrungsverhalten

Chemistry Plastics

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Chemistry Plastics

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1

Origin, Construction, Structure

Chemical Compound Molecule

From Crude Oil crude oil

diesel and heating oil other oils

PVC PE/PP PU/PS PA/UP

Destillation of fractionating tower

Crude Oil gases

Cracking from Benzine to Monomers

plastic 1 plastic 2 plastic 3

The Field of Plastics

Synthetic Plastics Modified Natural Materials

Polymerisates Polycondensates Polyadducts

Elastomeres Elastomeres Epoxidharz

Secondary Valency Forces

Difference between: amorphous - semicrystalline

Property amorphous semicrystalline

Shrinkage Values of some Thermoplastics

Elastomer, wide-mesh crosslinked

Distribution of Polymerchain Length

Distribution of the Polymer Chain Lengths

Size of the Macromolecules

The thickness of a macromolecule is about (2 or 3)/10.000.000 millimeters.

If we consider in thougt as a theoretical experiment that a molecule

It is spoken from macromolecules, if more than 1000 single molecules

Impact of the increasing Length of the

Together with elongation of the molecule

• higher toughness (Zähigkeit)

• higher chemical resistance

• worse flow characteristics

Dependency of the Properties

Forces within the Material

innermoleculare bonding forces

ET = softening point range temperature

State Diagram of Semicrystallite Thermoplastics

State Diagram Thermosettings

State Diagram of Elastomeres

ZT = decomposition temperature range

State Diagrams of several Thermoplastics

-100 - 50 0 50 100 150 200 250 300 350 400

General Properties of Plastics (1)

to the good properties belong:

– good electrical isolation property

– excellent resistance against chemicals and weathering

– little heat conductivity

General Properties of Plastics (2)

on the other hand there are:

– a big thermal expansion

– a small elastic-modulus (E-module)

– the time dependency of the mechanical

• niveau of the properties

• Creeping and flow

• nonlinearities (influence of the impact)

The molecule chains, additives and colours are

• high mass temperature • strength of the parts

Reasons Failures, Problems

• decompression too big or

Drying of the Material

Nützliche Infos aus Datenblättern

Temperatur δ °C Drücke bar

Kunststoffe werden durch ihren chemischen Namen

Jeder Hersteller stellt von einer Werkstoffart z. B. POM unter-

Ultraform Handelsname der Firma BASF für POM