DEFORMATION AND

FRACTURE OF POLYMERS
Monday, April 9, 2018
Wednesday, April 11, 2018
 Strengthening Techniques of Polymers

 Increasing crystallinity
For a specific polymer, increasing the degree of
crystallinity can enhance its mechanical properties, since
it affects the extent of the intermolecular secondary
bonding (van der walls bonds)
 stronger secondary bonding
 Crosslinking
Increasing the degree of crosslinking can strengthen the
polymer and make it more brittle, since it can inhibit
relative chain motion
 Strengthening Techniques of Polymers

 Increasing molecular weight

For relatively low molecular weight polymers, the
mechanical strength increase with molecular weight
 Tensile strength increase with molecular weight
 Deforming
One of the most important techniques used to improve
mechanical strength on a commercial basis is by
predeforming the polymer, so that it become oriented,
having the structure depicted in the following figure
(next slide)
 Adding Fillers
The influence of crystallinity and
molecular weight on Polyethylene
 Deformation of Semicrystalline
Polymers
 Many semicrystalline polymers in bulk form will have
the spherulitic structure
 Each spherulite consists of numerous chain-folded
ribbons, or lamellae, that radiate outward from the
center
 Deformation that occurs in semicrystalline polymer is
plastic deformation
 The mechanism of plastic deformation is best
described by the interactions between lamellar and
intervening amorphous regions in response to an
applied tensile load
Process Stages of Plastic Deformation
in Semicrystalline Polymers
 Process Stages of Plastic Deformation
in Semicrystalline Polymers
 Figure a shows two adjacent chain-folded lamellae and the
interlamellar amorphous material, prior to deformation
 During the initial stage of deformation (figure b), the
lamellar ribbon slide past one another as the tie chains
within the amorphous region become extended
 In the second stage of deformation (figure c), deformation
occurs by tilting of the lamellae so that the chain folds
become aligned with the tensile axis
 Figure d shows that crystalline block segments separate
from the lamellae, which segments remain attached to one
another by tie chains
 In the final stage (figure e), the blocks and tie chains
become oriented in the direction of the tensile axis
 Macroscopic Deformation of
Semicrystalline Polymers
 The macroscopic deformation
involves necking that start forming
at the upper yield point
 Within this neck, the chain become
oriented, which leads to localized
strengthening  continued
deformation at this point and
specimen elongation proceeds by
the propagation of this neck
region along the gauge length
 Different from ductile metals
where the deformation is
confined in the initial neck region Tensile stress-strain curve for
semicrystalline material
 Deformation of Elastomers
 One of the fascinating properties of the elastomeric
materials is their rubberlike elasticity
 Rubberlike elasticity relate to ability to be deformed
to quite large deformations, and then elastically
spring back to the original form
 This behavior was probably first observed in natural
rubber
 In an unstressed state, an elastomer will be
amorphous and composed of molecular chains that
are highly twisted, kinked, and coiled
 Deformation of Elastomers
 Elastic deformation, upon application of a tensile load, is simply the partial
uncoiling, untwisting, and straightening, and the resultant elongation of the
chains in the stress direction

 Upon release of the stress, the chains spring back to their prestressed
conformations, and the macroscopic piece returns to its original shape
 Deformation of Elastomers
 The driving force for elastic deformation is a
thermodynamic parameter called entropy
 Entropy is a measure of the degree of disorder within a
system  entropy increases with increasing disorder
 Upon release of the stress and the chains return to their
original kinked and coiled contours, the entropy increases
 Two intriguing phenomena result from this entropic effect
First, when streched, an elastomer experiences a rise in
temperature
Second, the modulus elasticity increase with increasing
temperature
 Fracture of Polymers
 The fracture strengths of polymeric materials are low
relative to those of metals and ceramics
 The fracture process is the formation of cracks at regions
where there is a localized stress concentration (i.e.,
scratches, notches, and sharp flaws)
 Covalent bonds in the network or crosslinked structure are
severed during fracture
 The mode of fracture in thermosetting polymers is brittle
 For thermoplastic polymers, both ductile and brittle
modes are possible  many of these materals are
capable of experiencing a ductile-to-brittle transition
 Fracture of Thermoplastic Polymers
 Factors that favor brittle fracture in thermoplastic polymers
are:
- Reduction in temperature
- Increase in strain rate
- The presence of a sharp notch
- Increase specimen thickness
- Modification of the polymer structure
 Glassy thermoplastic are brittle at relatively low
temperatures, otherwise as the temperature is raised, they
become ductile in the vicinity of their glass transition
temperature and experience plastic yielding prior to fracture
 Demonstrated by the stress-strain characteristics of PMMA
Stress-Strain Characteristics of PMMA

 At 4 C, PPMA is totally brittle, whereas at 60 C it

becomes, extremely ductile
 Fracture of Thermoplastic Polymers
 One phenomenon that frequently preceds fracture in
some glassy thermoplastic polymers is crazing
 Crazes are regions of very localized yielding, which
lead to the formation of small and interconnected
microvoids (Fig a)
 Fibrillar bridges form between these microvoids
wherein molecular chains become oriented (Fig a)
 If the applied tensile load is sufficient, fibrillar
bridges elongate and break, causing the microvoids
to grow and coalesce  as the microvoids coalesce,
cracks begin to form (Fig b)
 Plane Strain Fracture Toughness
 The susceptibility of polymers to fracture when a
crack is present may be expressed in terms of the
plane strain fracture toughness (KIC)
 The magnitude of KIC will depend on:
- Characteristic of polymer (i.e., molecular weight,
crystallinity, etc)
- Temperature
- Strain rate
- External environment
Plane Strain Fracture Toughness