Polymer

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Vulcanization

The treatment that accomplishes cross-linking of


elastomer molecules, so that the rubber
becomes stiffer and stronger but retains
extensibility
• On a submicroscopic scale, the long-chain
molecules of rubber become joined at certain
tie points, the effect of which is to reduce the
ability of the elastomer to flow
– A typical soft rubber has 1 or 2 cross-links per 1000
units (mers)
– As the number of cross-links increases, the
polymer becomes stiffer and behaves more and
more like a thermosetting plastic (hard rubber)

©2002 John Wiley & Sons, Inc.


M. P. Groover, “Fundamentals
of Modern Manufacturing 2/e”
Figure 14.4 - Effect of vulcanization on rubber molecules: (1) raw
rubber, and (2) vulcanized (cross-linked) rubber. Variations of (2)
include: (a) soft rubber, low degree of cross- linking; and (b) hard
rubber, high degree of cross-linking

©2002 John Wiley & Sons, Inc.


M. P. Groover, “Fundamentals
of Modern Manufacturing 2/e”
Thermosetting and Thermoplastic
Polymers
Determined by mechanical behavior upon heating to high
temperatures
Thermosetting Thermoplastic
•Thermosets •Thermoplasts
Become permanently hard Soften upon heating;
upon heating. Do not harden upon cooling. It is
soften upon subsequent reversible
heating Fabricated by applying
heat and pressure
Chapter 14: Polymer Structures 29
Thermosetting and Thermoplastic
Polymers continue…
Thermosetting Thermoplastic
Initial Heating: As Temperature is
increased
Covalent crosslink form and
link adjacent molecular Secondary bonds break
chains. Chains are anchored; (due to molecular
no vibrational or rotational motion). So when stress
chain motions, 10-50% of is applied, adjacent
chain mer units are cross- chains move
linked
Chapter 14: Polymer Structures 30
Thermosetting and Thermoplastic
Polymers continue…
Thermosetting Thermoplastic
Further heating: Irreversible
degradation upon
Severance (breaking) of
further heating:
crosslink bonds and polymer
degradation Violent molecular
vibrations break
primary covalent
bonds

Chapter 14: Polymer Structures 31


Thermosetting and Thermoplastic
Polymers continue…
Thermosetting Thermoplastic
Thermoset polymers are harder, Soft and Ductile
stronger and brittle
Most linear
polymers and
Better dimensional stability
polymers with
e.g., Cross linked and network branched structures
polymers with flexible
Vulcanized rubbers, epoxies and chains
phenolic and some polyester resins
Chapter 14: Polymer Structures 32

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