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The science of rubber materials

• A rubber, or elastomer, is a natural or synthetic


polymer which at room temperature can be
stretched repeatedly to at least twice its original
length and which after removal of the tensile
load will immediately return to approximately its
original length (ASTM standard definition).

• Typical values of Young modulus and strain at


break for common elastomers are 106 Pa and
103 % respectively.
Structural requirements
• The chains must be of high molecular weight, with presence
of many entanglements between the macromolecules

• The chains must be flexible, which means that the polymer


Tg must be low (below ambient temperature typically) as
well as their cohesive forces (low polarity polymers)

• Random coil conformation (high conformational disorder) is


assumed when the polymer is undeformed

• The final material must be slightly crosslinked, either


chemically (vulcanization) or physically (phase segregation
like in the case of thermoplastic elastomers)
Classification of Elastomers

• Natural rubber

• General purpose elastomers

• Specialty elastomers
Classification of Rubbers
• Natural rubber

1,4-cis-polyisoprene

• unsaturated (can be vulcanized with S)


• latex from Hevea Brasiliensis then coagulated
• natural polymer
→ great variety based on purity, viscosity, etc...
• modified NR (at latex stage)
→ epoxidized (ENR), deproteinized (DNR), oil-extended (OENR)
• high structural regularity → controlled stereochemistry
(> 99.9% 1,4 cis → strain-induced crystallization)
Classification of Rubbers
• General purpose rubbers (only C, H)

unsaturated (→ can be vulcanized)


• polybutadiene (BR)
• synthetic polyisoprene (IR)
• styrene-butadiene rubber (SBR)

BR IR SBR
Classification of Rubbers
• General purpose rubbers (only C, H)

saturated (→ cannot be vulcanized*)


• ethylene-propylene rubber (EPR)
• polyisobutylene-isoprene (butyl rubber - IIR)*
• ethylene-propylene-diene rubber (EPDM)*

*contain unsaturations at low concentrations (< 5%) → vulcanization

EPR / EPDM IIR


Classification of Rubbers
• Specialty elastomers (heteroatoms: Si, O, Cl, F, N)

• nitrile rubber (acrylonitrile-butadiene, NBR)


• polychloroprene (neoprene, CR)
• silicone rubbers (e.g., PDMS)
• fluorocarbon elastomers (co/ter-polymers of VDF, HFP, TFE)

NBR CR PDMS

VDF HFP TFE


• Enthalpic-elastic behavior: the imposed deformation causes an
increase in free energy of the material due to the increase of
internal energy / enthalpy of the material related to the
displacement of atoms from their equilibrium (minimum internal
energy) positions.
• Entropic-elastic behavior: the deformation causes only
conformational transitions in the polymer, with the chains
progressively passing from a compact, disordered, random
coil situation to a more ordered arrangement with chains
aligned in the direction of the imposed deformation.
Entropic elasticity
• Entropic elasticity is exhibited by elastomers:
the driving force to elastic retraction is the
entropy gain (∆S > 0) related to the random
coil conformation

• It is however needed that mechanical energy


is stored upon deformation without
dissipation (viscous flow) → vulcanization
non-crosslinked Entropic elasticity

final state
initial state under load under load
(stress released)
crosslinked