Chapter 1 - Plastics

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
Implementation of European Guidelines for Joining Technology Training, Project no.:2009-1-LEO05-03591

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
usually synthetic polymers. Implementation of European Guidelines for Joining Technology Training,
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
The number of the repeating units Project no.:2009-1-LEO05-03591
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.
INCPEN, Towards greener households, June 2001 p. 580.0400 A of the Chemical Economics Handbook

ACCENTURE RESEARCH, Trends in Manufacturing Polymers: Achieving High Performance in a Multi-Polar World, www.accenture.com
Nomenclature of polymer
1- Nomenclature Based on monomer source
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)-
2- Based on polymer structure

The most common method for condensation polymers since the polymer
contains different functional groups than the monomer
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)

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)

B. Classification by Monomer Composition
Homopolymers
Copolymers
Block
Graft
Alternating
Statistical
Homopolymers
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA
Homopolymer

Copolymers
Consist of two or more constitutional repeating units (A-B )
Several classes of copolymer are possible

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

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
e. Classification Based on Kinetics or Mechanism
Step-growth
Chain-growth
f. Classification by Application
Plastics
Fibers
Elastomers
Coatings
Adhesives

Main physical properties of polymers
1-Primary bonds : the covalent bonds that 8 - Glass transition temperature (Tg ) :
connect the atoms of the main chain temperature at which an amorphous
2- Secondary bonds : non covalent bonds polymer converts to a liquid or amorphous
that hold one polymer chain to domains of a semi crystalline polymer melt
another including hydrogen bond and other 9 Thermoplastics (plastics ) :polymers
dipole dipole attraction that undergo thermally reversible
3-Crystalline polymer : solid polymers with Interconversion between the solid state and
high degree of structural order and rigidity the liquid state
4- Amorphous polymers : polymers with a low 10- Thermosets : polymers that continue
degree of structural order reacted at elevated temperatures
5-Semi crystalline polymer : most polymers generating increasing number of crosslinks
actually consist of both such polymers do not exhibit
crystalline domains and amorphous domains melting or glass transition
with properties between that 11- Liquid crystalline polymers : polymers
expected for a purely crystalline or purely with a fluid phase that retains
amorphous polymer some order
6-Glass: the solid form of an amorphous 12- Elastomers : rubbery , stretchy
polymer characterized by rigidity and polymers the effect is caused by light
brittleness crosslinking that pulls the chains back to
7 Crystalline melting temperature (Tm): their original state
temperature at which crystalline polymers melt
Amorphous Crystalline
Glass phase (hard plastic)

9
8 Leathery phase
Log (stiffness)
7
6 Rubber phase (elastomer)
Pa
5
4 Liquid
3
Temperature
1.2
Polymers in the Solid State
Glass Transition Temperature

Crystalline Structure

POLYMERS IN THE SOLID STATE
Amorphous
Semi-crystalline
Glassy Rubbery

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.

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
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
stirring) Implementation of European Guidelines for Joining Technology Training,
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

1.4
Polyethylene
Principal Olefin Monomers

Mechanical Properties of Polyethylene
Physical Properties of Polyethylene

Principal Olefin Monomers
H H H H
Ethylene Propylene
C C C C
H H CH3 H
Poly n Poly n
H H H H
4-Methylpentene C C
Butene-1 C C
C2H5 H C5H6 H
Poly n Poly n
CH3
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 Medium High Linear High Density
Density Density Density
Density 0.91- 0.925 0.926- 0.94 0.941-0.95 0.959-0.965
Crystallinity 30% to 50% 50% to 70% 70% to 80% 80% to 91%
Molecular 10K to 30K 30K to 50K 50K to 250K 250K to 1.5M

Weight
Tensile 600 - 2,300 1,200 - 3,000 3,100 - 5,500 5,000 6,000
Strength, psi
Tensile 25K 41K 38K 75 K 150K 158 150K 158 K
Modulus, psi K
Tensile 100% - 650% 100%- 965% 10% - 1300% 10% - 1300%
Elongation, %
Impact Strength No break 1.0 no 0.4 4.0 0.4 4.0
ft-lb/in break
Hardness, Shore D44 D50 D50 D60 D60 D70 D66 D73

Physical Properties of Polyethylene
Physical Properties of polyethylene
Branched Low Medium Density High Linear High Density
Density Density
Optical Transparent to Transparent to Transparent to Transparent to opaque
opaque opaque opaque
Tmelt 98 115 C 122 124 C 130 137 C 130 137 C
Tg -100 C -100 C -100 C -100 C

H20 Absorption Low < 0.01 Low < 0.01 Low < 0.01 Low < 0.01
Oxidation Low, oxides Low, oxides Low, oxides readily Low, oxides readily
Resistance readily readily
UV Resistance Low, Crazes Low, Crazes Low, Crazes readily Low, Crazes readily
readily readily
Solvent Resistant Resistant below Resistant below 60C Resistant below 60C
Resistance below 60C 60C
Alkaline Resistant Resistant Resistant Resistant
Resistance
Acid Oxidizing Oxidizing Acids Oxidizing Acids Oxidizing Acids
Resistance Acids

1.5
Polypropylene
Polypropylene Structure
Advantages/Disadvatages of Polypropylene
Mechanical Properties of Polypropylene
Physical Properties of Polypropylene

Polypropylene Structure
H H
Propylene
C C
CH3 H
Isotactic- CH3 on one side of polymer chain (isolated).

Commercial PP is 90% to 95% Isotactic
H H H H H H H H H H
C C C C C C C C C C
CH3 H CH3 H CH3 H CH3 H CH3 H
Advantages/Disadvatages of Polypropylene
Advantages Disadvantages
Low Cost High thermal expansion
Excellent flexural strength UV degradation
Good impact strength Poor weathering resistance
Processable by all Subject to attack by
thermoplastic equipment chlorinated solvents and
Low coefficient of friction aromatics
Excellent electrical insulation Difficulty to bond or paint
Good fatigue resistance Oxidizes readily
Excellent moisture resistance flammable
Service Temperature to 126oC
Very good chemical resistance

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 Range of Range of MWD Range of MWD

Dispersity MWD MWD for for processing for processing
(Mw/Mn) processing
Tensile Strength, 4,500 5,500 600 - 2,300 5,000 6,000
psi
Tensile Modulus, 165K 225K 25K 41K 150K 158 K
psi
Tensile 100% - 600% 100% - 650% 10% - 1300%
Elongation, %
Impact Strength 0.4 1.2 No break 0.4 4.0
ft-lb/in
Hardness, Shore R80 - 102 D44 D50 D66 D73

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 -20 C -100 C -100 C

H20 0.01 0.03 Low < 0.01 Low < 0.01
Absorption
Oxidation Low, oxides Low, oxides Low, oxides readily

Resistance readily readily
UV Resistance Low, Crazes Low, Crazes Low, Crazes readily
readily readily
Solvent Resistant Resistant below Resistant below 60C
Resistance below 80C 60C
Alkaline Resistant Resistant Resistant
Resistance
Acid Oxidizing Oxidizing Acids Oxidizing Acids
Resistance Acids

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)
[11] Mori, S. and Barth, H. G., Size Exclusion Chromatography, Springer-
Verlag, 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., Wiley-
Interscience, 1992 (good treatment of polymer physics and properties)
[18] van Krevelen, D. W., Properties of Polymers, 3rd ed., Elsevier, 1990 (in-
depth 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


Chapter 1 - Plastics

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European Plastic Welder

Co ASR, Romanian Welding Society

Implementation of European Guidelines for Joining Technology Training, Project no.:2009-1-LEO05-03591

Implementation of European Guidelines for Joining Technology Training,

A typical polymer may include tens of

Polymers occur naturally in the form of

Single repeat unit: MONOMER

The field of synthetic polymers or

Also the macromolecular structure of

Implementation of European Guidelines for Joining Technology Training,

If X is a single word the name of polymer is written out

If X consists of two or more words parentheses should be

2- Based on polymer structure

Implementation of European Guidelines for Joining Technology Training,

Implementation of European Guidelines for Joining Technology Training,

Implementation of European Guidelines for Joining Technology Training,

Several classes of copolymer are possible

Linear chains :a polymer consisting of a single continuous chain of repeat units

Linear Branched Cross-linked Network

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

Implementation of European Guidelines for Joining Technology Training,

Implementation of European Guidelines for Joining Technology Training,

Glass phase (hard plastic)

Glass Transition Temperature

Implementation of European Guidelines for Joining Technology Training,

Implementation of European Guidelines for Joining Technology Training,

The glass transition, Tg, is temp. below

The Tg to a first approximation is a

For rubber bands: Tg = - 73C.

tougher, stiffer (due to stronger

Maximum service temperature

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Principal Olefin Monomers

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Crystallinity 30% to 50% 50% to 70% 70% to 80% 80% to 91%

Molecular 10K to 30K 30K to 50K 50K to 250K 250K to 1.5M

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Tg -100 C -100 C -100 C -100 C

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

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Crystallinity 30% to 50% 30% to 50% 80% to 91%

Molecular Weight 200K to 600K 10K to 30K 250K to 1.5M

Molecular Weight Range of Range of MWD Range of MWD

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Tg -20 C -100 C -100 C

Oxidation Low, oxides Low, oxides Low, oxides readily

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Implementation of European Guidelines for Joining Technology Training,

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