POLIMER

Dr. Kusmono

Lab Bahan Teknik

Departemen Teknik Mesin dan Industri
Fakultas Teknik Universitas Gadjah Mada
 Application Material Processing Method
Load-Bearing Glass-fiber reinforced Pressing of resin
- bumper beams polyester resins compounds
Moldings/covers Polyurathane Injection Molding
- front apron Polypropylene
- spoiler Polyethlene
- wheel-well liners
- radiator grill Acrylonitrile-butadiene-
- hood styrene (ABS)
- fenders Polycarbonate
- trunk
Protective Polyvinyl chloride Injection Molding/
Moldings Ethylene-Propylene Extrusion
Terpolymers
Energy Polyurethane Liquid Reaction
Absorbing Foam Foaming

Car Part Polymer

Trim Panels (3) Polypropylene (PP)
Impact Absorber Thermoplastic Olefin (TPO)
Radio Housing ABS/Polycarbonate(PC)
Door Outer Panel ABS/Polycarbonate(PC)
Handle Polypropylene (PP)
Fog Light Cover Thermoplastic Elastomeric
Olefin (TEO)
Tire Elastomers
ENGINE
⚫ Plastics vs. Metals
⚫ Polymer Applications in Automobiles
- Instrument Panels
- Engine
- Windows
- Tires
- Body Panels
 Why Design with Plastics?
• Light weight, high weight to • Relatively low cost
strength ratio, particularly compared to metals and
when reinforced composites

Density Cost
6
Why Design with Plastics?
⚫ Corrosion resistance
⚫ Low electrical and thermal conductivity, insulator
⚫ Easily formed into complex shapes, can be
formed, casted and joined.
⚫ Wide choice of appearance, colors and
transparencies

7
Disadvantages of using Plastics
⚫ Low strength
o
⚫ Low useful temperature range (up to 600 F)
⚫ Less dimensional stability over period of time
(creep effect)
⚫ Aging effect, hardens and become brittle over time
⚫ Sensitive to environment, moisture and chemicals
⚫ Poor machinability

8
Polimer

Definisi:

 Bahan yang memiliki struktur molekuler

yang sangat besar dan berikatan kovalen

 Bahan yang sebagian besar merupakan

senyawa organik

 Bahan yang terbentuk dari gabungan

monomer-monomer
Polimer

Polietilen
What is a polymer?
⚫ A long molecule
made up from lots of
small molecules
called
⚫ Monomers →
“struktur terkecil
yang berulang secara
periodik dan beratur
pada polimer”
All the same monomer
⚫ Monomers all same
type (A)
⚫ A+A+A+A→
⚫ -A-A-A-A-
⚫ eg poly(ethene)
polychloroethene
PVC
Different monomers
⚫ Monomers of two
different types A + B
⚫ A+B+A+B
⚫ → -A-B-A-B-
⚫ eg polyamides
⚫ polyesters
Homopolymer & Copolymer
Homopolymer:
 Polimer yang tersusun dari satu jenis
monomer

polyethylene)

Copolymer:
 Polimer yang tersusun dari lebih dari satu
jenis monomer berbeda
 Introduction to Polymer
⚫ Oligomer: Short polymer chain
⚫ Copolymer: polymer made up of 2 or more
monomers

⚫ Random copolymer: A-B-B-A-A-B-A-B-A-B-B-

B-A-A-B
⚫ Alternating copolymer: A-B-A-B-A-B-A-B-A-
B-A-B-A-B
⚫ Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-
B-B-B-B
 Copolymers Adapted from Fig.
14.9, Callister 7e.

two or more monomers random

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

A– B–
graft
Molekul Hidrokarbon
 Terdiri dari molekul hidrogen dan karbon

C2H4 (ethylene)
C2H2 (acetylene)

C3H8 (propane)
 Unsaturated hydrocarbon
⚫ 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
ISOMERISM = ISOMER
 Senyawa hidrokarbon yang memiliki
komposisi sama tetapi berbeda susunan
atomnya

C4H10 (butane)
C4H10 (isobutane)
ISOMERISM = ISOMER

ISOTACTIC

SINDIOTACTIC

RANDOM
 Degree of Polymerization, n
n = number of repeat units per chain
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 H ni = 6
H H H H H H H H H H H H
 Molecular Structures

• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.
Struktur Molekul Polimer
Struktur Molekul Polimer
Struktur Molekul Polimer
 Polymer Crystallinity
Adapted from Fig.
14.10, Callister 7e.
Ex: polyethylene unit cell

• Crystals must contain the

polymer chains in some way
– Chain folded structure

Adapted from Fig.

14.12, Callister 7e.
 Polymer Crystallinity
Polymers rarely exhibit 100% crystalline
• Too difficult to get all those chains aligned

crystalline
region
• % Crystallinity: how much
is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
amorphous
increases. 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.)
 Crystalline polymers
⚫ Areas in polymer where
chains packed in regular
way.
⚫ Both amorphous and
crystalline areas in same
polymer.
⚫ Crystalline - regular chain
structure - no bulky side
groups.
⚫ More crystalline polymer -
stronger and less flexible.
• Polymers tend to crystallize as they precipitate or are
cooled from a melt
• Acting to inhibit crystallization are their very large
molecules, often with complicated and irregular shapes,
which prevent efficient packing into ordered structures
• As a result, polymers in the solid state tend to be
composed of ordered crystalline domains and disordered
amorphous domains
• High degrees of crystallinity are found in polymers with
regular, compact structures and strong intermolecular
forces such as hydrogen bonds
– as the degree of crystallinity increases, the polymer
becomes more opaque due to scattering of light by
the crystalline regions
• Melt transition temperature, Tm: the temperature at
which crystalline regions melt
– as the degree of crystallinity increases, Tm increases
• Highly amorphous polymers are sometimes referred
to as glassy polymers
– because they lack crystalline domains that scatter
light, amorphous polymers are transparent
– in addition, they are weaker polymers, both in
terms of their high flexibility and low mechanical
strength
– on heating, amorphous polymers are transformed
from a hard glass to a soft, flexible, rubbery state
• Glass transition temperature, Tg: the temperature at
which a polymer undergoes a transition from a hard
glass to a rubbery solid
GLASS TRANSITION TEMPERATURE, Tg

Tg Tm

semicrystalline
log(Modulus)

crosslinked

T linear amorphous

Temperature
GLASS TRANSITION TEMPERATURE, Tg
AMORPHOUS SEMICRYSTALLINE
Degree of Crystallinity
There are many different factors that can determine the
amount of crystals or degree of crystallinity of a
plastic component.
• Cooling rate – If we cool the polymer more quickly,
we form fewer crystals
• Additives – some additives can be put into plastics
to increase the degree of crystallinity while others
can disrupt the formation of the crystals giving us a
lower degree of crystallinity
• Polymer type – different materials can form higher
or lower levels of crystallinity depending on their
molecular structure
PR
 Amorphous vs Semicrystalline

ITEM AMORPHOUS SEMICRYSTALLINE

Tm No Tm has Tm
Chemical resistance poor better

Optical properties better poor

Impact resistance better more brittle
Viscosity flow more easily
Weather resistance Better chemical resistance to
weathering effect
Shrinkage higher
Material Types
Amorphous
Polyvinyl Chloride (PVC)
Polycarbonate (PC)
Polymethylmethacrylate (PMMA or Acrylic)
Acrylonitrile Butadiene Styrene (ABS – a terpolymer)
 Semi-crystalline
Polyethylene (PE, HDPE, LDPE, etc.)
Polypropylene (PP)
Polyamides (PA – Nylon)
Polyesters
Polyethylene Terephthalate (PET)
Polybutylene Terephthalate (PBT)
Polyoxymethylene (POM - Acetal)
Polytetrafluoroethylene (PTFE – Teflon)
Polimer berdasar asal

A. Polimer Alami

B. Polimer Sintetis
Polimer Alami
Polimer yang berasal dari tanaman &
hewan yang telah digunakan selama
berabad-abad yang lalu

Contoh:
 Kayu
 Karet
 Cotton
 Wool
 Protein
 Enzim
 Sellulosa
• As Early as Life Began: natural polymers - BIOMACROMOLECULES
Polysaccharides: DNA, RNA, starch, cellulose, chitin, etc.

A-DNA Loop RNA Cellulose

Chitin

Proteins and Polypeptides Natural rubber

Hemoglobin Silk
Polimer Sintetis
Polimer yang hasil sintesa dari molekul
organik yang kecil

Karakter:
 Murah Contoh:
 Sifat dapat ❖ Plastik
diatur dan lebih ❖ Serat sintetis
unggul dari
polimer alamiah
• As Broad as in Daily Life: synthetic polymers

polystyrene cis-polyisoprene

polycarbonate poly(vinyl chloride)

Sifat Polimer
Analog seperti logam & keramik, sifat
polimer = f (unsur penyusun polimer)

Monomer:
 Struktur terkecil yang berulang secara
teratur & periodik pada polimer
Monomer dan Polimer

polytetrafluoroethylene

Polyvinyl chloride

Polypropylene
Ikatan Kovalen

SINGLE DOUBLE TRIPLE

Ikatan Kovalen

A. UNSATURATED
 molekul yang memiliki ikatan
kovalen double dan triple

B. SATURATED
 molekul yang memiliki ikatan
kovalen single
 POLYMER SYNTHESIS

⚫ There are two major classes of polymer formation mechanisms

⚫ Addition polymerization: The polymer grows by sequential
addition of monomers to a reactive site
⚫ Chain growth is linear

⚫ Maximum molecular weight is obtained early in the reaction

⚫ Step-Growth polymerization: Monomers react together to make

small oligomers. Small oligomers make bigger ones, and big
oligomers react to give polymers.
⚫ Chain growth is exponential

⚫ Maximum molecular weight is obtained late in the reaction

 ADDITION POLYMERIZATION

There are 3 distinct stages: initiation, propagation, and

termination
an active center capable of propagation is
Initiation ➔ formed by a reaction between an initiator
(or catalyst) species and the monomer unit

Example: PE

R. : Initatior or catalist
. : Unpaired electron
R and R’ → represent
organic radicals—groups of
atoms that remain as a
single unit and maintain
their identity during
chemical reactions.
Examples of singly bonded
hydrocarbon radicals include
the CH3, C2H5 , and C6H5
(methyl, ethyl, and phenyl)
groups.
ADDITION POLYMERIZATION

Propagation ➔ involves the linear growth of the

molecule as monomer units become attached to
one another in succession to produce the chain
molecule
ADDITION POLYMERIZATION

Termination ➔ the active ends of two propagating

chains may react or link together to form a
nonreactive molecule
STEP-GROWTH POLYMERIZATION

Step-growth or Condensation polymerization is

the formation of polymers by stepwise
intermolecular chemical reactions that
normally involve more than one monomer
species; there is usually a small molecular
weight by product such as water, which is
eliminated. No reactant species has the
chemical formula of the mer repeat unit, and
the intermolecular reaction occurs every time a
mer repeat unit is formed
❖ reaction times for condensation are
generally longer than for addition
polymerization
STEP-GROWTH POLYMERIZATION

Example: Polyester from reaction ethylene glycol

and adipic acid
POLYMERIZATION

Addition Polymerization:
❖ PP
❖ PS
❖ PVC

Step-growth Polymerization:
❖ Thermosetting polyester
❖ Phenol formaldehyde
❖ Nylon
❖ Polycarbonate
POLYMERIZATION
Karakteristik Umum Polimer
✓ Ringan (ρ = 1 – 1,7 g/cm3)
✓ Mampu cetak/bentuk baik
✓ Sensitip terhadap suhu, laju regangan, dan
sifat kimia lingkungan pemakaian
✓ Isolator yang baik
✓ Ketahanan terhadap air dan zat kimia sangat
baik
✓ Produk dengan sifat yang berbeda dapat
dibuat tergantung pada cara pembuatannya
✓ Murah
✓ Kurang tahan terhadap panas
✓ Kekerasannya lebih rendah daripada logam
dan keramik
✓ Mudah termuati listrik secara elektrostatik
Karakteristik Mekanik Polimer
1) Sifat tarik

2) Sifat bending

3) Sifat compress/tekan

4) Kekuatan impak

5) Kekerasan

6) Ketahanan aus dan gesek

7) Ketahanan lelah
Kekuatan Tarik
Kekuatan Tarik
Ketahanan aus dan gesekan Polimer

Logam:
✓ Koefisien gesek hampir konstan
tidak tergantung beban, luas bidang
kontak, dan laju gesekan

Polimer:
✓ Koefisien gesek tergantung beban,
luas bidang kontak, dan laju
gesekan
Ketahanan fatik/lelah

Dipengaruhi oleh:
✓ Temperatur
T  ➔ ketahanan lelah 

✓ Frekuensi
f  ➔ ketahanan lelah 
KLASIFIKASI POLIMER

A. TERMOPLASTIK

B. TERMOSET

C. ELASTOMER
TERMOPLASTIK
Jenis polimer yang apabila dipanaskan
akan melunak dan mencair, serta jika
didinginkan akan mengeras. Proses ini
dapat diulang (“reversible”)

Sifat:
✓ Relatif lunak dan ulet
✓ Proses pembuatan dgn menerapkan
pemanasan dan tekanan bersama-
sama
✓ Sebagian polimer linear + beberapa
polimer cabang
Thermoplastics (80%)

⚫ No cross links between chains.

⚫ Weak attractive forces between chains
broken by warming.
⚫ Change shape - can be remoulded.
⚫ Weak forces reform in new shape when cold.
TERMOPLASTIK

Contoh:
✓ PE (polyethylene)
✓ PP (polypropylene)
✓ PS (polystyrene)
✓ PC (polycarbonat)
✓ PVC (polyvinyl chloride)
✓ PA (polyamide/nylon)
Commodity vs Engineering Plastics
PE
Karakteristik:
✓ Murah
✓ Isolator
✓ Tangguh
✓ Low friction coefficient
✓ Good flexibility
✓ Excellent corrosion resistance
✓ Low strength and poor resistance
to wheathering
Aplikasi: flexible bottles, electrical
insulation, chemical tubing,
toys, and film wrapping
materials
PP
Karakteristik:
✓ Ringan ( = 0,90-0,92 gr/cm3)
✓ Murah
✓ Isolator
✓ Excellent fatigue strength
✓ Chemically inert
✓ Poor resistance to UV light
✓ Mampu cetaknya baik

Aplikasi: bottles, packing film, TV

cabinets,
NYLON
Karakteristik:
✓ Good mechanical strength
✓ Good abrasion resistance
✓ Toughness
✓ Low coefficient friction
✓ Good dimension stability
✓ Absorb waters

Aplikasi: bearing, gear, cam, handle,

jacketing for wires and cable
POLYSTYRENE (PS)

Karakteristik:
✓ Inexpensive
✓ Excellent electrical properties and
optical clarity
✓ Good thermal and dimensional
stability

Aplikasi: battery cases, toys, indoor

lighting panels, gelas
PVC

Karakteristik:
✓ Inexpensive
✓ Ordinary rigid
✓ Susceptible to heat distortion

Aplikasi: pipe, electrical wire insulation,

floor covering
ABS

Karakteristik:
✓ Outstanding strength and toughness
✓ Resistance to heat distortion
✓ Good electrical properties
✓ Flammable and soluble in some organic
solvents

Aplikasi: automotive components, helmets,

tool handles, luggage
 POLYCARBONATE (PC)

CHEMICAL STRUCTURE:

PHYSICAL PROPERTIES:
⚫ Density =  = 1.20 – 1.22 g/cm 3
⚫ Water absorption (0.16–0.35%)
THERMAL PROPERTIES:
⚫ Radiation resistance = fair
⚫ Melting temperature (Tm) = 267°C
⚫ Ultraviolet resistance = fair
⚫ Glass transition temperature (Tg) = 150°C
⚫ Thermal conductivity (k) at 23°C = 0.190.22 W/(m·K)
⚫ Specific heat capacity (c) =1.2-1.3 kJ/(kg·K)
APPLICATIONS OF POLYCARBONATE (PC)

❖ Vandal resistant windows

❖ Machine guards
❖ Outdoor signs
❖ Sky lights
❖ Backboards
❖ Bike, roller blading
protective wear
TERMOSET
Jenis polimer yang apabila dipanaskan
akan mengeras secara permanen, dan
tidak akan melunak jika dipanaskan
berlanjut. Proses ini dapat tidak dapat
diulang (“irreversible”)

Sifat dibanding termoplastik:

✓ Lebih keras
✓ Lebih kuat dan getas
✓ Memiliki kestabilan dimensi
yang lebih baik
✓ Lebih baik ketahanan panas
✓ Tahan terhadap larutan kimia
Thermosets

⚫ Extensive cross-linking formed by

covalent bonds.
⚫ Bonds prevent chains moving relative
to each other.
⚫ What will the properties of this type of
plastic be like?
Longer chains make stronger polymers

⚫ Critical length needed before

strength increases.
⚫ Hydrocarbon polymers
average of 100 repeating
units necessary but only 40
for nylons.
⚫ Tensile strength measures
the forces needed to snap a
polymer
GLASS TRANSITION TEMPERATURE, Tg

related to chain mobility

⚫ increased flexibility, lower Tg

factors :
⚫ flexible links in backbone

⚫ size of pendent groups

⚫ interaction between chains

⚫ plasticizers interfere with bonding,
increase chain movement, decrease Tg
RESIN EPOKSI
Karakteristik:
➢ Excellent combination of mechanical
properties and corrosion resistance
➢ Low shrinkage, low toxicity
➢ Dimensionally stable
➢ Good adhesion & Relatively inexpensive
➢ Good electrical properties (insulation)

Aplikasi: electrical molding, adhesive,

protective coating, dan sebagai
bahan matrik komposit
Types of epoxy resin

▪ Phenolic glycidyl ethers (DGEBA)

▪ Aromatic glycidyl amines (TGMDA)
▪ Cycloaliphatics (Diglycidyl Ester of Hexahydrophthalic Acid,
DGEHA)

DGEBA

DGEHA
TYPES OF EPOXY CURING AGENTS/HARDENER
Epoxy-amine cross-linking through the reaction of
the amine group with the epoxide group.

Amine hardener

Epoxy resin

Epoxy resin: Amine hardener = 2:1 atau 1:1

RESIN PHENOLIC/FENOL

Karakteristik:
➢ Excellent thermal stability to
over 150C
➢ Inexpensive

Aplikasi: motor housing, telephones,

electrical fixtures
RESIN POLYESTER

Karakteristik:
➢ Murah
➢ Excellent electrical properties
➢ Low to high temperature use
➢ Good as matrix for composites

Aplikasi: helmet, fiberglass boat, auto

body components, chairs, fan
 ELASTOMER
• Elastomers are rubber like polymers that are thermoset or
thermoplastic
– butyl rubber: natural rubber
– thermoset: polyurethane, silicone
– thermoplastic: thermoplastic urethanes (TPU), thermoplastic
elastomers (TPE), thermoplastic olefins (TPO), thermoplastic
rubbers (TPR)
• Elastomers exhibit more elastic properties versus plastics which
plastically deform and have a lower elastic limit.
• Rubbers have the distinction of being stretched 200% and returned to
original shape. Elastic limit is 200%
SILICONE RUBBER