YIELD AND FRACTURE IN

POLYMERS
Juan Baselga
(jbaselga@ing.uc3m.es)
Room 1.1 A 13

1
 General considerations
70
Glassy, brittle
*

Semicrystalline below Tg
Stress (MPa) *
35
Semicrystalline above Tg
*
ductile
Elastomer

Strain (%) 100

Glassy polymers: brittle (in tension) linear elastic (modulus up to 3GPa) up to failure
below  5%. In compression some polymers present ductility.
Semicrystalline: below Tg, brittle, non-linear elastic up to failure
Semicrystalline: above Tg undergo yield, extensive plastic deformation (shear yielding,
strain softening, cold drawing) and even strain hardening in some occasions
Elastomers: modulus  1 MPa, extend reversibly up to 500% (entropy spring); strain
induced crystallization

In any case, mechanical behavior strongly depends upon temperature and rate of testing:
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viscoelastic effects
 Theoretical modulus
Theoretical modulus of elasticity can be calculated b
for fully extended polymer single chains. 
It consists of calculating the force needed to extend 

the bond length and the bond angle 1

assuming that the force constants for both are given b cos   cos2  b 2 sen 2  
E    
by and , and dividing by the chain cross Am  kb 4k  
section.
AC E  GPa / E

Good agreement with X-ray (GPa)

determination for crystalline 2
(nm ) Th. Exp. Th. Th.
polymers (single crystals).
Polyethylene 0.183 186-347 250 32.5 0.096
Semicrystalline or amorphous Polyethylene terephtalate 0.200 122-146 140 - -
polymers exhibit much lower
it-Polypropylene 0.343 42 35 3.9 0.093
values : the modulus in these
does not depend on bond at-Polyvinyl chloride 0.286 200 - 18.2 0.091
parameters but on Polyamide 66 0.203 200 - 16.9 0.085
intermolecular forces. Polytetrafluoroethylene 0.277 156 - 15.3 0.098
it-Polystyrene 0.698 12 - 1.4 0.117

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H.G Elias. “Introduction to polymer science” VCH, 1997
 Theoretical strength
Fracture involves the creation of new surfaces in a body. In a polymer occurs by the
breaking of primary (covalent) and secondary bonds (e.g. van der Waals or H-bonds).
Several approaches to calculate strength.
- Chain scission: rupture of chemical bonds crossing a given area AC . The simplest one.
- Theory of rate processes: covalent bonds are broken if thermal fluctuations around a
bond exceed a critical value
- Theory of Frenkel: the dependence of stress on bond distance is assumed to be a
sinusoidal function.
AC E  / E
Last column shows : . GPa
(GPa)
Experimental values for of 2
conventionally processed (nm ) Theory Experim. TheoryTheory
polymers are 1000 times lower Polyethylene 0.183 186-347 250 32.5 0.096
than prediction. Failure must be Polyethylene terephtalate 0.200 122-146 140 - -
associated to imperfections it-Polypropylene 0.343 42 35 3.9 0.093
at-Polyvinyl chloride 0.286 200 - 18.2 0.091
Perfectly oriented and packed chains Polyamide 66 0.203 200 - 16.9 0.085
would present very high stiffness and Polytetrafluoroethylene 0.277 156 - 15.3 0.098
strength along the chain axis:  the it-Polystyrene 0.698 12 - 1.4 0.117
search for polymers with rigid
backbone that can be spun into fibers
4
H.G Elias. “Introduction to polymer science” VCH, 1997
 Theoretical strength
3-4 GPa attainable upper limit due to imperfections.
Polymer fibers compare well with carbon, boron and steel
fibers where strength/weight ratio is important

T300, T50, P100: carbon fibers; Spectra 1000: gel spun PE

SSE PE: solid state extruded PE

PBO:

(poly(p-phenylene benzobisoxazol))

Kevlar 49
(poly(p-phenylene terphtalamide))

S.J Krause et col. Polymer 29(1988)1354

5
 Plastic deformation

Two main mechanisms:

• Yielding (shear yielding)
• Homogeneous deformation
• Inhomogeneous deformation
• Necking
• Shear bands
• Crazing

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 Plastic deformation
• Yielding or shear yielding consists of a change of shape
without significant change in volume

• Limits strength of a polymer if brittle fracture can be

suppressed (Yield stress)
• If homogeneous yielding does occur the polymer is
likely to be tough
• Shear yielding in the form of microshear bands plays
a key role in crack initiation
• Even for brittle fracture, there is localised shear
yielding (and crazing) at the crack tip

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 Yielding
General definition of Yield Stress: is the minimum
Fracture stress at which permanent strain is produced when
the stress is subsequently removed. For polymers
sometimes a maximum at low strains is observed
but not always: yield stress.

Linear elastic: homogeneous def.

At yield: neck forms; inhomogeneous def.
Yield
Cold drawing Strain softening: yield stress of a local region is
Strain softening
Strain succeeded; neck stabilizes
hardening
Cold drawing: neck increases in length by
extracting polymer from un-necked region of
Strain ()
sample; chain orientation
Strain hardening: chain orientation
Stress ()

When no maximum appears:

- Intersection of two tangents
- Intersect of a parallel line to the initial linear
0.02 Strain () portion of the curve offset a given amount,
typically 2%
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 Yielding: necking
At low stresses samples deform uniformly until a
maximum stress is attained.

Sometimes, a neck or deformation band is produced:

plastic deformation is concentrated entirely or
primarily in a small region of the specimen.
The neck may be stable or not. If stable, extensive
non-uniform deformation at low stress appears: cold
drawing: chain disentanglement and orientation
I.M Ward et col “ An introduction to mechanical
properties of solid polymers” Wiley (2004)
Necking implies a reduction of nominal cross-section:
better studied in terms of true stress.
Let us define :
load
and the initial cross-sectional area and gage length,
nominal stress
true stress
elongation or draw ratio
If plastic deformation occurs at constant volume (common) . Since ,
then . The true stress is now given by . 9
 Yielding: Considère construction
The maximum in the nominal stress-strain curve is defined by the condition . .

/( ) /

This equation states that the slope of the true stress versus elongation at the yield point
(necking) must be a straight line without independent term i.e. that passes through the origin in
a plot of versus .

True stress 𝜎

-1 0 1 2
Strain
0 1 2 3
Draw ratio 10
 Yielding: Considère construction
The general shape of the stress-strain curve for
Region 3 polymers consists of three regions.
Region 1: elastic region where stress rises linearly
(approx.) with strain.
True stress 𝜎

Region 2: a maximum stress is achieved: yield

stress. Stress increases then less steeply or a fall in
true stress can occur: strain softening. Initiation of
Region 2 a neck:
Region 1 • fluctuation in material properties may cause a
localized reduction in yield stress
-1 0 1 2 • An element has a lower effective cross-sectional
Strain
area
0 1 2 3 In both cases, they yield at a lower tension than
Draw ratio applied.

Region 3: localized deformation continues until strain hardening (chain orientation) appears.
The highly strained element can not strain more. To accommodate further extension, more
elements are brought to their yield point and the neck propagates along the length of the
sample. https://www.youtube.com/watch?v=y3UWhhymSj8 11
https://www.youtube.com/watch?v=I28m4FZzqro&wide
 Yielding: Considère construction
The Considère construction is useful as a criterion to decide whether a polymer will neck or
will neck and cold-draw. Four cases

Case I: is always greater than . The

I II polymer extends uniformly and no neck is
formed.
𝜎
𝜎

Case II: Neck is formed but gets steadily

thinner until fracture occurs
-1 0 1 2 -1 0 1 2
Case III: Two tangents. Neck is formed and
IV becomes stable. After strain softening cold
III
drawing appears.
𝜎

Case IV: The same as Case III but without

strain softening

-1 0 1 2 -1 0 1 2

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 Molecular theories of yielding
Glassy polymers. Eyring theory of rate processes
• It has been suggested ( 1950) that the load drop on the load-extension curve may be
attributed to adiabatic heating. Local rise has been measured and strongly depends on
strain rate . Strain softening may be a consequence of temperature rise. BUT
necking is also observed under quasistatic conditions where
• It has also been suggested ( 1958) that yielding is consequence of viscous flow induced by
mechanical tension. Eyring theory of viscous flow
A certain energy barrier must be exceeded
for a polymer segment to jump to a vacant
position.
In the relaxed non-stressed state, jump
frequency is given by an Arrhenius law

Vacant position
If load is applied, mechanical work is
Polymer segment
used to decrease the potential energy barrier
where is a certain area unit and is the jump distance.
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 Molecular theories of yielding
Glassy polymers. Eyring theory of rate processes.
∆
In the stressed state, jump frequency is . has units of
volume and represents the volume a polymer segment must displace for plastic deformation to
occur . Polymer segments can return back to their original positions with frequency
∆
. The net flux of jumps will be in the forward
direction, which must be equal to the rate at which deformation takes place.
∆
Therefore for high stresses. This equation can be rearranged as
∆ ̇
.A plot of against at constant T should give parallel straight lines

Although the physical significance of and

remains obscure, modifications of this equation have
successfully modeled the effect of hydrostatic
pressure on yield stress.
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I.M Ward “Mechanical properties of solid polymers” Wiley (1983)
 Molecular theories of yielding
Glassy polymers. Other theories.
Robertson (1966). In a polymer there is an equilibrium fraction of cis-trans
conformations separated by an energy difference . On application of a
stress this energy difference becomes reduced by the work done by the
shear component of stress. Great volume change

Argon (1973). Deformation consists in

the formation of a pair of kinks:
coupled change of conformations
(TTTG+TG-TTT). Low volume change.
Resistance arises from elastic
interactions with neighbor chains

Theories appear to fit yield stress dependence on

deformation rate on both tension and compression and the
effect on hydrostatic pressure (Robertson) and the
temperature dependence of shear stress (Argon) 15
 Plastic deformation
Shear bands in glassy polymers.
Polycarbonate Polyethylene terephtalate Polystyrene

R. Quinson, et col. J. Mat. Sci., 32, 1997, R.N Haward (Editor), “The physics of glassy polymers” Appl. Sci. Pub. London,1973
1371 – 1379,

Appear in glassy polymers and is associated to strain softening, particularly in compression

 1m thick.
Appear at an angle 45º if there is no change in volume (maximum shear).
If material dilates (expansion) the angle may increase
Bands posses a fine structure consisting of 20 – 100 nm fibrous morphology

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Plastic deformation
Semicrystalline polymers.

a) Elongation of chains from

amorphous phase
b) Tilting of chains from lamellar
region
c) Separation of block segments
of lamellar region
d) Orientation of both chain
segments and crystalline
blocks

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 Crazing

They are microvoids with microfibrils connecting the surfaces that grow perpendicularly to
the tensile axis
Initiation of crazes usually takes place at the surface of specimen: scratches, dust particles or
other inhomogeneities.
Crazes grow by extrusion of microfibrils until a crack is formed: considerable energy
adsorption in craze initiation, growth and breakdown
Important because they are precursors of brittle fracture 18