POLYMER

4 DESEMBER 2019
Ancient Polymer History
Originally many natural polymers were used
◦ Wood – Rubber
◦ Cotton – Wool
◦ Leather – Silk
◦ Protein
◦ Enzymes Animals
◦ Cellulose
Polymer
What is a polymer?

Poly Mer
Polymer : Plastics and rubber
Many Repeat unit
repeat repeat repeat
unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
Polymer
Polymers are synthesized by joining many small molecules together to form very
large molecules, called macromolecules, that possess a chain-like structure

Small units → Monomer

Ex : sintesis Poliethilene
Molecular Structures
• Covalent chain configurations and strength:

secondary
bonding

Linear B ranched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

 Copolymers random

Copolymers are polymers whose molecules are made of repeating units

of two different types. Ex : ethylene-propylene (-(C2H4)n (C3H6)m-)

alternating
two or more monomers polymerized together
random – A and B randomly vary in chain
block
alternating – A and B alternate in polymer chain
block – large blocks of A alternate with large blocks of B
graft – chains of B grafted on to A backbone

graft Adapted from Fig.

A– B– 14.9, Callister 7e.
Copolymer
Example : ABS plastics → Acrylonitrile-Styrene-Butadiene (Thermoplastic Polymer)
Acrylonitrile 15-35%
Styrene 40 – 60 % Graft Copolymer
Butadiene 5 – 50 %
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C
(we also recognize Si-H ‘silicones’)
Saturated hydrocarbons
◦ Each carbon bonded to four other atoms

H H
H
C C CnH2n+2
H H
H
Unsaturated Hydrocarbons
Double & triple bonds relatively reactive – can form new bonds
◦ Double bond – ethylene or ethene - CnH2n
H H
C C
H H
◦ 4-bonds, but only 3 atoms bound to C’s
◦ Triple bond – acetylene or ethyne - CnH2n-2

H C C H
 Polymer Crystallinity
Polymers rarely exhibit 100% crystalline crystalline
region
Too difficult to get all those chains aligned

% Crystallinity: how much is crystalline.

-- TS and E often increase with % crystallinity.
-- Annealing causes crystalline regions to grow.
% crystallinity increases.
amorphous
Ex : polyethylene, nylon region

Adapted from Fig. 14.11, Callister 6e.

(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of Materials, Vol. III,
Mechanical Behavior, John Wiley and Sons, Inc., 1965.)
Polymer Crystallinity
the degree of crystallinity (the proportion of crystallized material in the mass) is
always less than 100%. As crystallinity is increased in a polymer, so are
1. density,
2. stiffness, strength, and toughness,
3. heat resistance
4. if the polymer is transparent in the amorphous state, it becomes opaque when
partially crystallized.
Polymer Crystallinity
Types of Polymers
• Polymers can be separated into plastics and rubbers
• As engineering materials, it is appropriate to divide them
into the following three categories:
1. Thermoplastic polymers
2. Thermosetting polymers
3. Elastomers
where (1) and (2) are plastics and (3) are rubbers
Thermoplastic Polymer (TP)
• Material padat pada Temperatur ruang tetapi menjadi lunak ketika dipanaskan hanya pada
beberapa ribu derajat → mudah untuk dibuat menjadi sebuah produk
• Dapat dipanaskan dan didinginkan kembali tanpa terjadi kerusakan (degradation) ex : daur ulang
• Ulet dan struktur → little crosslinking
– ex: polyethylene, polypropylene, polystyrene, polyvinylchloride, nylon
Polietilena (PE) = Botol plastik, mainan, bahan cetakan, ember, drum, pipa saluran, isolasi kawat dan
kabel, kantong plastik dan jas hujan.
Polipropena (PP) = karung, tali, botol minuman, serat, bak air, insulator, kursi plastik, alat-alat rumah
sakit, komponen mesin cuci, pembungkus tekstil, dan permadani.
Polistirena = Insulator, sol sepatu, penggaris, gantungan baju.
Polivinilklorida (PVC) = pipa air, pipa plastik, pipa kabel listrik, kulit sintetis, bungkus makanan, sol
sepatu, sarung tangan dan botol detergen.
 Thermoplastic Polymer (TP)
Sifat mekanik (pada temperature ruang) :
1. Kekakuan lebih rendah, sehingga modulus elastisitasnya 2 atau 3 kali lebih rendah
daripada logam dan keramik.
2. Tensile strength rendah 10% dari logam
3. Kekuatan lebih rendah dibanding logam dan keramik
4. Keuletan lebih besar, tetapi ada kisaran nilai keluletan yang sangat besar, 1%
kemuluran (elongation) untuk polystyrene sampai 500% atau lebih untuk
polypropylene
5. Sifat mekaniknya bergantung pada temperature → Tg dan Tm
Thermoplastic Polymer (TP)
Sifat Fisik :
1. Densitas rendah dibandingkan logam dan keramik – densitas polimer sekitar
1.2, keramik 2.5 dan logam 7.0.
2. Koefisien muai panas lebih besar – sekitar 5 kali lebih tinggi disbanding logam
dan 10 kali lipat untuk keramik
3. Titik leleh rendah
4. Konduktivitas panas rendah dibandingkan logam
5. Sifat isolator listrik yang baik. Polimer dapat dibuat menjadi konduktor
apabila dicampur dengan bahan lain seperti logam dan karbon
Thermosets Polymer (TS)
• Tidak dapat dipanaskan dan didinginkan kembali seperti thermoplastic
• Ketika dipanaskan, polymer menjadi lunak dan mengalir mengikuti bentuk cetakan,
tetapi pada temperature tinggi menghasilkan rekasi kimia dan mengeraskan
material menjadi padat yang tidak dapat melebur (infusible solid)
• Keras , getas dan kaku (tidak fleksibel), modulus elastisitasnya 2-3 kali lebih besar
• Jika dipanaskan kembali polymer akan rusak
• Struktur → large crosslinking (10-50 % mers)
ex: urethane, epoxy, bakelit, melamin, polyester
Bakelit → saklar listrik
Melamin → ubin lantai, peralatan dapur
 Elastomers (E)
• Polymer yang sangat elastis ketika tegangan mekanik sangat rendah
• Beberapa elastomer dapat meregang (factor 10) dan dapat kembali ke bentuk
semula
• Mempunyai sifat yang berbeda dengan polymer thermoset tetapi struktur
molekul hampir sama dan berbeda dengan polymer termoplastik
• Ex : karet alam berasal dari alam dan karet sintetis yang dihasilkan dari proses
polimerisasi

Picture : Model of long

elastomer molecules,
with low degree of cross-
linking: (a) unstretched,
and (b) under tensile
stress.
Commercial Thermoplastics
❑ Acetals (polyoxymethylene)
Properties → high stiffness, strength, toughness, wear resistance, high melting point, low
moisture absorption, and is insoluble in common solvents at ambient temperatures.
Applications : door handles, pump housings, machinery components
❑ Acrylics
The most important thermoplastic in the acrylics group is polymethylmethacrylate (PMMA) or
Plexiglas (Rohm & Haas’s trade name for PMMA) (transparant). Examples include automotive
tail-light lenses, optical instruments, and aircraft windows.
❑ Acrylonitrile – Butadiene –Styrene (ABS)
ABS is a two-phase terpolymer, one phase being the hard copolymer styrene–acrylonitrile, while
the other phase is styrene-butadiene copolymer that is rubbery.
Commercial Thermoplastics
1. Cellulosics
2. Fluoropolymers
3. Polyamides
4. Polyester
5. Polyethylene
6. Polypropylene
7. Polystyrene
8. Polyvinylchloride (PVC)
Commercial Thermosets
1. Amino Resins
2. Epoxies
3. Phenolics
4. Polyimides
5. Polyurethanes
6. Silicones
 brittle polymer
Mechanical Properties
i.e. stress-strain behavior of polymers FS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

• Fracture strengths of polymers ~ 10% of those for metals

• Deformation strains for polymers > 1000%
– for most metals, deformation strains < 10%

Adapted from Fig. 15.1, Callister 7e.

The influence of temperature on the stress–strain characteristics
of poly(methylmethacrylate).

Consider the stress–strain behavior for

poly(methyl methacrylate) (Plexiglas) at several
temperatures between 4C and 60C. Increasing
the temperature produces
(1) a decrease in elastic modulus,
(2) a reduction in tensile strength, and
(3) an enhancement of ductility—at 4C (40F)
the material is totally brittle, whereas there is
considerable plastic deformation at both 50C
and 60C.
Schematic tensile stress–strain curve for a semicrystalline polymer.
Specimen contours at several stages of deformation are included.
Tensile Response: Brittle & Plastic
Near Failure (MPa) fibrillar
structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

e
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from
Figs. 15.12 & 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, Prentice-
Hall, Inc., 1974, pp. 500-501.)
Tensile Response: Elastomer Case
(MPa)
x brittle failure

Stress-strain curves adapted

plastic failure from Fig. 15.1, Callister 7e.
x Inset figures along elastomer
curve (green) adapted from Fig.
x 15.15, Callister 7e. (Fig. 15.15 is
elastomer from Z.D. Jastrzebski, The
Nature and Properties of
final: chains Engineering Materials, 3rd ed.,

e are straight,
still
John Wiley and Sons, 1987.)

cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
 Polymer Types: Plastics
Plastics – Thermoplastic and Thermosetting
They have a wide variety of combinations of properties.
➢ Some plastics are very rigid and brittle
➢ Others are flexible, exhibiting both elastic and plastic deformations when stressed and
sometimes experiencing considerable deformation before fracture.
➢ All molecular structures are liniar or branched. However, to be considered plastics,
linear or branched polymers must be used below their glass transition temperatures (if
amorphous) or below their melting temperatures (if semicrystalline), or they must be
crosslinked enough to maintain their shape.
Polymer Types: Elastomers
Elastomers – rubber
Crosslinked materials
◦ Natural rubber → Latex
◦ Synthetic rubber
- SBR- styrene-butadiene rubber :which is used predominantly in automobile tires, reinforced
with carbon black. styrene

butadiene

– Silicone rubber
Polymer Additives
Improve mechanical properties, processability, durability, etc.
Fillers
◦ Added to improve tensile and compressive strength, abrasion resistance,
toughness & thermal stability.
◦ ex: carbon black, silica gel, wood flour, glass fiber, limestone, etc.
• Plasticizers
o The flexibility, ductility, and toughness of polymers may be improved
o Their presence also produces reductions in hardness and stiffness.
o commonly added to PVC - otherwise it is brittle
o Applications : tubing, raincoat
Polymer Additives
• Stabilizers
◦ Antioxidants
◦ UV protectants
• Colorants
– Dyes or pigments
The molecules in a dye actually dissolve in the polymer. Pigments are filler
materials that do not dissolve but remain as a separate phase;
• Flame Retardants
The flammability of polymeric materials is a major concern, especially in the manufacture of
textiles and children’s toys.
 Processing Plastics - Molding
Compression molding
◦ Thermoplastic (more time-consuming and expensive) or thermoset

• There are two mold. Both mold pieces are

heated; however, only one is moveable.
• The mold is closed, and heat and pressure
are applied, causing the plastic to become
viscous and flow to conform to the mold
shape.
• Before molding, raw materials may be
mixed and coldpressed into a disc, which is
called a preform.
• Preheating of the preform reduces molding
time and pressure, extends die lifetime,
and produces a more uniform finished
Adapted from Fig. 15.23, Callister 7e. (Fig. 15.23 is from F.W. Billmeyer, Jr., piece.
Textbook of Polymer Science, 3rd ed.,John Wiley & Sons, 1984. )
Processing Plastics - Molding
Injection molding
◦ thermoplastic & some thermosets

Adapted from Fig. 15.24,

Callister 7e. (Fig. 15.24 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 2nd edition,
John Wiley & Sons, 1971. )
Processing Plastics - Molding
Processing Plastics – Molding
Extrusion

Adapted from Fig. 15.25,

Callister 7e. (Fig. 15.25 is from
Encyclopædia Britannica, 1997.)
 Polymer Recycling
❑ Recycling means recovering the discarded plastic items and reprocessing them into
new products, in some cases products that are quite different from the original
discarded items.
❑ There are several reasons that plastics are difficult to recycle :
1. Compared to plastic parts, metal items are much larger and heavier
2. Compared to plastics, which come in a variety of chemical compositions that do not
mix well, glass products are all based on silicon dioxide
3. Many plastic products contain fillers, dyes, and other additives that cannot be
readily separated from the polymer itself.
 Biodegradable Polymer
Plastics that are decomposed by the actions of microorganisms occurring in nature,
such as bacteria and fungi.
▪ partially biodegradable plastics
consist of a conventional polymer and a natural filler. The polymer matrix is
petroleum-based, which is non-biodegradable, but the natural filler can be consumed
by microorganisms → sponge-like structure
▪ completely biodegradable plastics
consisting of a polymer and filler that are both derived from natural and renewable
sources. Ex : A common filler used in bioplastics is cellulose, often in the form of
reinforcing fibers in the polymer-matrix composite.
There are several reasons for the commercial and technological importance of polymers:
➢ Plastics can be formed by molding into intricate part geometries, usually with no further
processing required. They are very compatible with net shape processing.
➢ Plastics possess an attractive list of properties for many engineering applications where
strength is not a factor: (1) low density relative to metals and ceramics; (2) good strength-to-
weight ratios for certain (but not all) polymers; (3) high corrosion resistance; and (4) low
electrical and thermal conductivity.
➢ On a volumetric basis, polymers are cost competitive with metals.
➢ On a volumetric basis, polymers generally require less energy to produce than metals. This is
generally true because the temperatures for working these materials are much lower than for
metals.
➢ Certain plastics are translucent and/or transparent, which makes them competitive with glass
in some applications.
➢ Polymers are widely used in composite materials