European Plastic Welder

Chapter 1: Plastics
Co ASR, Romanian Welding Society
P1 CWS, Czech Welding Society ANB
P2 SLV, Schweisstechnische Lehr- und Versuchsanstalt SLV Duisvurg, Niederlassung der GSI mbH
P3 IIS, Italian Welding Institute
P4 EWF, European Federation for Welding, Joining and Cutting
P5 ISQ, Institute for Welding and Quality
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1.1
Generals on Polymers

Definitions
Application of polymers
Nomenclature of polymers
Classification of polymers
Main physical properties of polymers

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Introduction to polymers
Term polymer: greek poli (many) + meros (unit) = many units
Polymers are a large class of materials
consisting of many small molecules
(called monomers) that can be linked
together to form long chains, thus they are
known as macromolecules (term
introduced by H. Staudinger in 1920s).
A typical polymer may include tens of
thousands of monomers. Because of their
large size, polymers are classified as
macromolecules.
Polymers occur naturally in the form of
proteins, cellulose(plants), starch(food)
and natural rubber.
Engineering polymers, however, are
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Definitions
Polymer
Large molecule consisting of a number of repeating units with molecular
weight typically several thousand or higher
Repeating unit
The fundamental recurring unit of a polymer
Monomer
The smaller molecule(s) that are used to prepare a polymer
Oligomer
A molecule consisting of reaction of several repeat units of a monomer but
not large enough to be consider a polymer
Single repeat unit: MONOMER
Many repeat units: POLYMER
Degree of polymerization
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Application of polymers
The field of synthetic polymers or
plastics is currently one of the fastest
growing materials industries. The
interest in engineering polymers is
driven by their manufacturability,
recyclability, mechanical properties,
and lower cost as compared to many
alloys and ceramics.
Also the macromolecular structure of
synthetic polymers provides good
biocompatibility and allows them to
perform many biomimetic tasks that
cannot be performed by other
synthetic materials, which include
drug delivery, use as grafts for
arteries and veins and use in artificial
tendons, ligaments and joints.

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Application of polymers

INCPEN, Towards greener households, June 2001

p. 580.0400 A of the Chemical Economics Handbook

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Application of polymers

ACCENTURE RESEARCH, Trends in Manufacturing Polymers: Achieving High Performance in a Multi-Polar World, www.accenture.com

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Nomenclature of polymer
Nomenclature Based on monomer source- 1
The addition polymer is often named according to the monomer that was
used to form it
Example : poly( vinyl chloride ) PVC is made from vinyl chloride
-CH2-CH(Cl)
If X is a single word the name of polymer is written out
directly
- ex. polystyrene
-CH2-CH(Ph)
Poly-X
If X consists of two or more words parentheses should be
used
- ex , poly (vinyl acetate ) -CH2-CH(OCOCH3)
Based on polymer structure- 2
The most common method for condensation polymers since the polymer
contains different functional groups than the monomer
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Nomenclature of polymers
PC =
Polycarbonat
PPE = Polyphenylether
SMA = Styrol-Maleinsureanhydrid
ABS = Acrylnitril-Butadien-Styrol
PMMA = Polymethylmethacrylat
PS =
Polystyrol
SAN = Styrol-Acrylnitril-Copolymere
PVC = Polyvinylchlorid
PET = Polyethylenterephthalat (PETP)
PBT = Polybutylenterephthalat (PBTP)
PA =
Polyamid
POM = Polyoxymethylen
RF-PP = Resorcin-Formaldehyd-Polypropylen
PE-UHMW = Polyethylen-ultra high molecular weight
PP =
Polypropylen
PE-HD = Polyethylen hoher Dichte (High Density)
PE-LD = Polyethylen niedriger Dichte (Low Density)
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Classification of polymers
Main classifications of the polymers:
by origin
by Monomer composition
by chain structure
by thermal behaviour
by kynetics or mechanism
by application

A. Classification by Origin
Synthetic organic polymers
Biopolymers (proteins, polypeptides, polynucleotide, polysaccharides, natural
rubber)
Semi-synthetic polymers (chemically modified synthetic polymers)
Inorganic polymers (siloxanes, silanes, phosphazenes)

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B. Classification by Monomer Composition

Homopolymers
Copolymers
Block
Graft
Alternating
Statistical

Homopolymers
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA

Homopolymer

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Copolymers
Consist of two or more constitutional repeating units (A-B )
Several classes of copolymer are possible
Statistical copolymer (Random)
ABAABABBBAABAABB
two or more different repeating unit
are distributed randomly
Alternating copolymer
ABABABABABABABAB
are made of alternating sequences
of the different monomers
Block copolymer
AAAAAAAAABBBBBBBBB
long sequences of a monomer are followed
by long sequences of another monomer
Graft copolymer
AAAAAAAAAAAAAAAAAA
B
B
B
B
B
B
Consist of a chain made from one type of
monomers with branches of another type

Statistical

Alternating

Block

Graft

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c. Classification by Chain structure (molecular architecture)

Linear chains :a polymer consisting of a single continuous chain of repeat units
Branched chains :a polymer that includes side chains of repeat units connecting
onto the main chain of repeat units
Hyper branched polymer consist of a constitutional repeating unit including a
branching groups
Cross linked polymer :a polymer that includes interconnections between chains
Net work polymer :a cross linked polymer that includes numerous
interconnections between chains

Linear

Branched

Cross-linked

Network

Direction of increasing strength

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d. Classification by Thermal Behavior

Polymers may be classified as follows, according to the mechanical response at
elevated temperatures:

Thermoplasts

Thermosets.
a) Thermoplasts:
Thermoset polymers soften when heated and harden when cooled. Simultaneous
application of heat and pressure is required to fabricate these materials.
On the molecular level, when the temperature is raised, secondary bonding forces
are diminished so that the relative movement of adjacent chains is facilitated
when a stress is applied.
Most Linear polymers and those having branched structures with flexible chains are
thermoplastics.
Thermoplastics are very soft and ductile.
The commercial available thermoplasts are

Polyvinyl Chloride (PVC) and Polystyrene

Polymethyl methacrylate

Polystyrene
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Classification by Thermal Behavior

b) Thermosets:
Thermosetting polymers become soft during their first heating and become
permanently hard when cooled. They do not soften during subsequent heating.
Hence, they cannot be remolded/reshaped by subsequent heating.
In thermosets, during the initial heating, covalent cross-links are formed between
adjacent molecular chain. These bonds anchor the chains together to resist the
vibration and rotational chain motions at high temperatures. Cross linking is
usually extensive in that 10 to 15% of the chain mer units are cross linked. Only
heating to excessive temperatures will cause severance of these crosslink
bonds and polymer degradation. Thermoset polymers are harder, stronger, more
brittle than thermoplastics and have better dimensional stability.
They are more usable in processes requiring high temperatures
Most of the cross linked and network polymers which include
Vulcanized rubbers

Epoxies
Phenolic
Polyester resins

are thermosetting polymers.

Thermosets cannot be recycled, do not melt, are usable at higher temperatures
than thermoplastics, and are more chemically inert
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e. Classification Based on Kinetics or Mechanism

Step-growth
Chain-growth
f. Classification by Application
Plastics
Fibers
Elastomers
Coatings
Adhesives

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Main physical properties of polymers

Primary bonds : the covalent bonds that-1
connect the atoms of the main chain
Secondary bonds : non covalent bonds- 2
that hold one polymer chain to
another including hydrogen bond and other
dipole dipole attraction
Crystalline polymer : solid polymers with-3
high degree of structural order and rigidity
Amorphous polymers : polymers with a low- 4
degree of structural order
Semi crystalline polymer : most polymers-5
actually consist of both
crystalline domains and amorphous domains
with properties between that
expected for a purely crystalline or purely
amorphous polymer
Glass: the solid form of an amorphous-6
polymer characterized by rigidity and
brittleness
7 Crystalline melting temperature (Tm):
temperature at which crystalline polymers melt

8 - Glass transition temperature (Tg ) :

temperature at which an amorphous
polymer converts to a liquid or amorphous
domains of a semi crystalline polymer melt
9 Thermoplastics (plastics( :polymers
that undergo thermally reversible
Interconversion between the solid state and
the liquid state
10- Thermosets : polymers that continue
reacted at elevated temperatures
generating increasing number of crosslinks
such polymers do not exhibit
melting or glass transition
11- Liquid crystalline polymers : polymers
with a fluid phase that retains
some order
12- Elastomers : rubbery , stretchy
polymers the effect is caused by light
crosslinking that pulls the chains back to
their original state

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Amorphous

Crystalline
Glass phase (hard plastic)

9
8
7
Log (stiffness)
6
Pa

Leathery phase
Rubber phase (elastomer)

5
4

Liquid

Temperature
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1.2
Polymers in the Solid State

Glass Transition Temperature

Crystalline Structure

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POLYMERS IN THE SOLID STATE

Amorphous

Semi-crystalline

Glassy

Rubbery

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Glass Transition Temperature

The glass transition, Tg, is temp. below
which a polymer OR glass is brittle or
glass-like; above that temperature the
material is more plastic.
The Tg to a first approximation is a
measure of the strength of the secondary
bonds between chains in a polymer; the
stronger the secondary bonds; the
higher the glass transition temperature.
Polyethylene Tg = 0C;
Polystyrene = 97 C
PMMA (plexiglass) = 105 C.
Since room temp. is < Tg for PMMA, it is
brittle at room temp.
For rubber bands: Tg = - 73C.
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Crystallinity
Crystallization in linear polymers: achieving a very regular arrangement
of the mers
Induction of crystallinity
cooling of molten polymer
evaporation of polymer solution
annealing heating of polymer at a specific temperature
drawing stretching at a temperature above Tg
Effects:

Increased Density
Increases Stiffness (modulus)
Reduces permeability
Increases chemical resistance
Reduces toughness

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Crystalline polymers (vs amorphous polymers)

tougher, stiffer (due to stronger
interactions)
higher density, higher solvent
resistance (due to closely packing
morphology)
more opaque (due to light
scattering by crystallites)
Crystalline morphologies
Spherulite aggregates of small fibrils in a radial pattern (crystallization
under no stress)
Drawn fibrillar obtained by drawing the spherulitic fibrils
Epitaxial one crystallite grown on another; lamella growth on long
fibrils; the so-called shish-kebab morphology (crystallization under
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1.3
.Characteristics of polymers
Behaviour in exploitation

Maximum service temperature

Coefficient of friction
Flammability
Tensile strengh at break
Coefficient of linear expansion
Thermal guidelines

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1.4
Polyethylene

Principal Olefin Monomers

Mechanical Properties of Polyethylene
Physical Properties of Polyethylene

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Principal Olefin Monomers

Ethylene

Poly

Butene-1

Poly

Propylene

Poly

C2H5

4-Methylpentene

Poly

CH3

H
n

C5H6

CH3

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Mechanical Properties of Polyethylene

Type 1: (Branched) Low Density of 0.910 - 0.925 g/cc

Type 2: Medium Density of 0.926 - 0.940 g/cc
Type 3: High Density of 0.941 - 0.959 g/cc
Type 4: (Linear) High Density to ultra high density > 0.959
Mechanical Properties
Branched Low
Density
Density
0.91- 0.925

Medium
Density
0.926- 0.94

High
Density
0.941-0.95

Linear High Density

0.959-0.965

Crystallinity

30% to 50%

50% to 70%

70% to 80%

80% to 91%

Molecular
Weight
Tensile
Strength, psi
Tensile
Modulus, psi
Tensile
Elongation, %
Impact Strength

10K to 30K

30K to 50K

50K to 250K

250K to 1.5M

600 - 2,300

1,200 - 3,000

3,100 - 5,500

5,000 6,000

25K 41K

38K 75 K

150K 158 K

100% - 650%

100%- 965%

150K 158
K
10% - 1300%

No break

1.0 no
break
D50 D60

0.4 4.0

0.4 4.0

D60 D70

D66 D73

ft-lb/in

Hardness, Shore D44 D50

10% - 1300%

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Physical Properties of Polyethylene

Physical Properties of polyethylene
Branched Low Medium Density
Density
Optical
Transparent to Transparent to
opaque
opaque
Tmelt
98 115 C
122 124 C

High
Density
Transparent to
opaque
130 137 C

Linear High Density

Transparent to opaque
130 137 C

Tg
-100 C
H20 Absorption Low < 0.01

-100 C
Low < 0.01

-100 C
Low < 0.01

-100 C
Low < 0.01

Oxidation
Resistance
UV Resistance

Low, oxides
readily
Low, Crazes
readily
Resistant
below 60C
Resistant

Low, oxides
readily
Low, Crazes
readily
Resistant below
60C
Resistant

Low, oxides readily

Low, oxides readily

Low, Crazes readily

Low, Crazes readily

Resistant below 60C

Resistant below 60C

Resistant

Resistant

Oxidizing
Acids

Oxidizing Acids

Oxidizing Acids

Oxidizing Acids

Solvent
Resistance
Alkaline
Resistance
Acid
Resistance

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1.5
Polypropylene

Polypropylene Structure
Advantages/Disadvatages of Polypropylene
Mechanical Properties of Polypropylene
Physical Properties of Polypropylene

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Polypropylene Structure

Propylene

CH3

Isotactic- CH3 on one side of polymer chain (isolated).

Commercial PP is 90% to 95% Isotactic

CH3 H

CH3 H

CH3 H

CH3 H

CH3 H

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Advantages/Disadvatages of Polypropylene

Advantages
Low Cost
Excellent flexural strength
Good impact strength
Processable by all
thermoplastic equipment
Low coefficient of friction
Excellent electrical insulation
Good fatigue resistance
Excellent moisture resistance
Service Temperature to 126oC
Very good chemical resistance

Disadvantages
High thermal expansion
UV degradation
Poor weathering resistance
Subject to attack by
chlorinated solvents and
aromatics
Difficulty to bond or paint
Oxidizes readily
flammable

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Mechanical Properties of Polypropylene

Mechanical Properties of Polypropylene
Polypropylene LDPE
HDPE
(For Comparison) (For Comparison)
Density
0.90
0.91- 0.925
0.959-0.965
Crystallinity

30% to 50%

30% to 50%

80% to 91%

Molecular Weight

200K to 600K

10K to 30K

250K to 1.5M

Molecular Weight
Dispersity MWD
(Mw/Mn)
Tensile Strength,
psi
Tensile Modulus,
psi
Tensile
Elongation, %
Impact Strength

Range of
MWD for
processing
4,500 5,500

Range of MWD
for processing

Range of MWD
for processing

600 - 2,300

5,000 6,000

165K 225K

25K 41K

150K 158 K

100% - 600%

100% - 650%

10% - 1300%

0.4 1.2

No break

0.4 4.0

R80 - 102

D44 D50

D66 D73

ft-lb/in

Hardness, Shore

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Physical Properties of Polypropylene-Polyethylene

Physical Properties of Polypropylene
Polypropylene LDPE
HDPE
Optical
Transparent to Transparent to
Transparent to opaque
opaque
opaque
Tmelt
175 C
98 115 C
130 137 C
Tg
H20
Absorption

-20 C
0.01 0.03

Oxidation
Low, oxides
Resistance
readily
UV Resistance Low, Crazes
readily
Solvent
Resistant
Resistance
below 80C
Alkaline
Resistant
Resistance
Acid
Oxidizing
Resistance
Acids

-100 C
Low < 0.01

-100 C
Low < 0.01

Low, oxides
readily
Low, Crazes
readily
Resistant below
60C
Resistant

Low, oxides readily

Oxidizing Acids

Oxidizing Acids

Low, Crazes readily

Resistant below 60C
Resistant

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Reference
1] Billmeyer, F. W., Textbook of Polymer Science, 3rd ed., Interscience Publishers,
1984 (classic book with excellent treatment of polymer properties)
[2] Barth, H. G. and Mays, J. W., Eds., Modern Methods of Polymer
Characterization, Wiley, 1991 (covers latest developments at the time of most
methods)
[3] Brady, Jr., R. F., Ed., Comprehensive Desk Reference of Polymer
Characterization and Analysis, American Chemical Society-Oxford, 2003 (survey of
characterization and analytical methods)
[4] Brandrup, J., Immergut, E. H. ,Grulke, E. A., Abe, A, and Bloch, D. R., Eds.,
Polymer Handbook, 4th ed., John Wiley and Sons, 2005 (premier handbook of
polymer science, listing virtually all polymer characteristics for most polymers)
[5] Brydson, J. A., Plastics Materials, Butterworth Heinemann, 2000
(comprehensive treatment of plastics, their synthesis, properties, and applications)
[6] Bueche, F., Physical Properties of Polymers, Krieger Publishing, 1979
(emphasis is on polymer physics)
[7] Cowie, J.M.G. and Arrighi, V., Polymers: Chemistry and Physics of Modern
Materials, 3rd ed., CRC Press 2008 (excellent discussion of physical properties
and applications)
[8] Heimenz, P.C. and Lodge, T. P., Polymer Chemistry, 2nd ed., CRC Press, 2007
(comprehensive treatment of polymer chemistry - synthesis and physical chemistry)
[9] Mark, J.E., Allcock, H. R., and West, R., Inorganic Polymers, Oxford, 2005
(physical chemistry and properties of inorganic polymers)
[10] Mark, J. E., Ed., Polymer Data Handbook, Oxford, 1999 (compilation of major
classes of polymers and their physical properties)
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[11] Mori, S. and Barth, H. G., Size Exclusion Chromatography, SpringerVerlag, 1999 (comprehensive treatment of SEC, theory and applications)
[12] Munk, P. and Aminabhavi, T. M., Introduction to Macromolecular Science,
2nd ed., John Wiley and Sons, 2002 (emphasis on polymer physical chemistry)
[13] Nielsen, L. E., Polymer Rheology, Marcel Dekker, 1977 (introductory text
on polymer rheology)
[14] Richardson, T. L. and Lokensgard, E., Industrial Plastics: Theory and
Applications, Delmar, 1996 (practical overview of some important properties
and polymer processing)
[15] Carraher, Jr., C. E., Seymour/Carraher's Polymer Chemistry, 7th ed., CRC
Press, 2007 (popular introduction to polymer chemistry)
[16] Seymour, R. B., Engineering Polymer Sourcebook, McGraw Hill, 1990
(good overview of physical properties of engineering polymers)
[17] Sperling L. H., Introduction to Physical Polymer Science, 2d d., WileyInterscience, 1992 (good treatment of polymer physics and properties)
[18] van Krevelen, D. W., Properties of Polymers, 3rd ed., Elsevier, 1990 (indepth treatment of polymer properties, best resource available)
[19] Whistler, R., Industrial Gums, 2nd ed., Academic Press, 1973 (although
outdated, gives solid background on the chemistry and properties of cellulosics
and polysaccharides)
[20] Wu, C. S., Ed., Handbook of Size Exclusion Chromatography, 2nd ed.,
Marcel Dekker, 2003 (covers all aspects of this important technique).
[21] Course: Classes of Polymeric Materials, Joe Greene, CSU, CHICO
[22] Course: Engineering Thermoplastics, Joe Greene, CSU, CHICO
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