2013-10-17 Deformation of Polymers PDF

Mechanical
Properties of
Polymers
Kamyar Davoudi
October, 2013
Materials Science Seminar
Definition of Polymers
•  Polymers are materials consisting of very long molecules ,

made up of hundreds or thousands repeating chemical
units (the monomer units), covalently bonded together.
•  Organic glasses
•  The long molecules are bonded together by
–  Ven der Waals
–  Hydrogen bonds
–  Covalent cross-‐links
Degree of Polymerization (DP):
the number of monomer units in a molecule.
Amorphous & Crystalline

Classes of Polymers
•  Thermoplastics: such as PE. soften on heating
•  Thermosets: such as epoxy. Harden when
two components are heated together
•  Elastomers or rubbers
•  Natural polymers: such as cellulose, lignin,
and protein
Thermoplastics
•  Commonest: Polyethylene (PE)
•  Often described as linear polymers (chains are
not cross linked)
•  T ñ secondary bonds melt, flow like viscous
liquid
•  Polystyrene (PS): amorphous
PE: partly crystalline H H
C C
•  Sub-‐units (monomers) of most of them
H R
Thermosets
•  Are made by mixing two components (resin and
hardener) à react and harden at RT or on heating
•  Heavily cross-‐linked à also called network polymers
•  T ñ secondary bonds melt, E drops à rubber

•  T ññ à decomposes
Elastomers
•  Almost linear polymers with occasional cross-‐links
•  only in noncrystalline
•  the backbone of the chain must be very long and have many kinks and
bends.
H H
C C C
H R H
•  At RT, secondary bonds have already melted

•  Vulcanization
•  Cross-‐links provide the memory of the material so that it returns to its
original shape
Elastomers
•  Helical pattern to the chain because of carbon-‐carbon double bonds

•  Mechanical Model: a highly coiled skeleton of primary bonds (including

cross-‐links) immersed in a viscous like medium.
•  During applica,on of a tensile load: coils are unwound to an extent
•  Upon unloading, the cross-‐linking atoms act to restore the original
dimensions.
•  No links, no restora,on

Elastomers
•  Elastic behavior of rubbers is different
from that of crystalline material
•  Only at extensions where the chains

approximately fully extended does
the force begin to stretch primary
bonds
•  decrease in S à Increase in F (free

energy)
•  Potential energy is unchanged
•  No primary bond stretching à small

modulus
Source: Courtney, Mechanical Behavior of Materials, 2000

Elastomers
•  Akin to ideal gases (no
change in poten,al
energy) but …
•  Incompressible

•  Neo-‐Hookean μ=NkBT
N : no. polymer chains/V

Glass Transi,on Temperature
Deforma,on of Polymers
•  Elastomers à Always elas,c response
•  Thermosets à viscoelas,c response
•  Thermoplas,cs à elas,c or plas,c
Change of Young’s modulus for linear
polymers
Linear-‐amorphous polymers (like PMMA & PS) show five regims of deforma,on
In general
ß Fixed loading ,me

Source: Ashby & Jones, Engineering Materials 2, 1998.

Glassy Regime and secondary
relaxa,ons
•  T<<Tg
E1~103 GPa
E2~ 1 GPa

Glass or visco-‐elas,c transi,on
•  T>Tg Extra free volume

lowers the packing density
•  S,ll there are some non-‐

sliding parts
•  On unloading the elas,c
regions pull the polymer to
its orgiginal shape
•  Modeled by springs and

dashpots
Higher Temperatures
•  Rubbery behavior
–  DP<103 àpolymer becomes s,cky liquid
–  DP>104àlong molecules intertwined like a jar of very long
worms àrubbery behavior
•  Viscous flow
•  Decomposi,on
–  the thermal energy exceeds the cohesive energy of some parts
of the molecular chain, causing degrada,on or
depolymeriza,on.
–  PMMA à decomposes into monomer units
–  PE àrandomly degrade into many products
Modulus Diagram for Polymers

The influence of Cross-‐linking on a contour of the modulus
diagram for polyisoprene

The effect of Temperature on Deformation

PMMA
Strength decreases and elonga,on
increases with higher temperature
Source: Gibson & Ashby, Cellular solids-‐structure &
Source:Carswell & Nason, ASTM Symposium on Plas,cs, Philadelphia, 1944
proper,es, Pergamon Press, Oxford, 1988
Briile Fracture
•  Polymers are briile at
T<~0.75 Tg
•  Pre exis,ng cracks lel by
machining or abrasion or
caused by environmental
aiack
•  Fracture toughness
KIC ~ 1 MPa m ½
•  Crack size a ~ O(μm)
•  σ ~ 1 MPa
Cold Drawing
At ε ~ 0.1
The chains unfold (if folded) or
draw out of the amorphous
tangle (if glassy)
For λ sufficient enough (2-‐4)

(ε=100-‐300%) : alignment of
molecules
à neck propagates until it is
all drawn

Crazing
•  Craze || maximum stress
•  Propagates along a
direc,on perpendicular to
the principle axis
•  Depends on T
(PE & PP draw at RT, PS
does not, but it crazes)
•  No crazing in compression
•  Precursor to fracture

Shear Banding
Highly localized

In the direc,on of maximum shear
stresses

More easily formed in tension

Crazing and shear banding
compete with each other
Source:McClintock & Ashby, Mechanical Behavior of Materials, 1966

Glassy Polymers: Thermoplas,cs
Micro-‐shear bands

At-‐Polystyrene at 22° C under compression Crazes
(Op,cal Microscopy w/ Polarized Light) At-‐Polystyrene in tension
(TEM)
Source: hip://www.files.chem.vt.edu/chem-‐dept/marand/Lecture23.pdf
Deforma,on of Crystalline Polymers
•  Crystalline polymers always contain some remnant non-‐
crystalline material.
Crystallization
Crystallization increases the modulus too


Summary
•  Polymers may be amorphous or semi-‐crystalline
•  Deforma,on of polymers is highly affected by temperature,
,me, DP, etc.
•  Elastomers deform elas,cally over a long range of
temperature
•  Linear polymers may be glassy, leathery, rubbery or viscous
flow
•  Plas,c behavior of linear polymers may cause by cold
drawing, crazing or shear banding
•  Crystalline polymers always have remnants of amorphous
polymers
•  The tension and compression behavior of polymers can be
quite different
Glass Transi,on Temperature

2013-10-17 Deformation of Polymers PDF

Uploaded by

Copyright:

Available Formats

2013-10-17 Deformation of Polymers PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2013-10-17 Deformation of Polymers PDF

Uploaded by

Copyright:

Available Formats

Mechanical

• Polymers are materials consisting of very long molecules ,

Amorphous & Crystalline

• Heavily cross-­‐linked à also called network polymers

• T ñ secondary bonds melt, E drops à rubber

• At RT, secondary bonds have already melted

• Mechanical Model: a highly coiled skeleton of primary bonds (including

• No links, no restora,on

• Only at extensions where the chains

• decrease in S à Increase in F (free

• No primary bond stretching à small

Source: Courtney, Mechanical Behavior of Materials, 2000

Source: Courtney, Mechanical Behavior of Materials, 2000

Source: Ashby & Jones, Engineering Materials 2, 1998.

Source: Ashby & Jones, Engineering Materials 2, 1998.

• T>Tg Extra free volume

• S,ll there are some non-­‐

• Modeled by springs and

Source: Ashby & Jones, Engineering Materials 2, 1998.

Source: Ashby & Jones, Engineering Materials 2, 1998.

For λ suﬃcient enough (2-­‐4)

Source: Ashby & Jones, Engineering Materials 2, 1998.

• No crazing in compression

• Precursor to fracture

Source:McClintock & Ashby, Mechanical Behavior of Materials, 1966

Source: Ashby & Jones, Engineering Materials 2, 1998.

Crystallization increases the modulus too

Source: Courtney, Mechanical Behavior of Materials, 1998

You might also like

•  Polymers are materials consisting of very long molecules ,

•  Heavily cross-‐linked à also called network polymers

•  T ñ secondary bonds melt, E drops à rubber

•  At RT, secondary bonds have already melted

•  Mechanical Model: a highly coiled skeleton of primary bonds (including

•  No links, no restora,on

•  Only at extensions where the chains

•  decrease in S à Increase in F (free

•  No primary bond stretching à small

•  T>Tg Extra free volume

•  S,ll there are some non-‐

•  Modeled by springs and

For λ suﬃcient enough (2-‐4)

•  No crazing in compression

•  Precursor to fracture