Lecture 28

Viscoelasticity
Failure in materials

Prof. Divya Nayar

Department of Materials Science and Engineering
[email protected]
Recap… 7.10

Fi
co
24%CW be
• True stress-strain curve 600
st
0%
4%CW
• Strengthening mechanisms: strain
500
0%CW
hardening, solid solution hardening, grain

Stress (MPa)
400
size reduction
300

• Lattice strains
200

100

0
0 0.05 0.1 0.15 0.2 0.25
Strain

stress–strain behavior of a low-carbon steel is shown in Fig

 tween 48 and 410 GPa (7 ! 106 to 60 ! 106 psi). M
polymers are about 100 MPa (15,000 psi)—for some m
psi).And, whereas metals rarely elongate plastically to
Stress-strain curve for Polymers elastic polymers may experience elongations to great
In addition, the mechanical characteristics of poly
15.2 Stress–Strain Behavior • 525
Three categories to temperature changes near room temperature. Cons
for poly(methyl methacrylate) (Plexiglas) at several
10 Figure 15.1 The
stress–strain behavior for
Figur
• Fibres (A) 60
A Brittle
8
brittle (curve A), plastic
(curve B), and highly
curve
how y
50 elastic (elastomeric) deter
TS
• Plastics (B) (curve C) polymers.

Stress (103 psi)

!y
6
Stress (MPa) 40
Plastic

Stress
• Elastomers (C) 30
B 4

20
Elastomer 2
10
C
Strain
0 0
0 1 2 3 4 5 6 7 8
Strain

same manner as for metals (Section 6.6). For plastic polymers (curve B, Figure 15.1),
the yield point is taken as a maximum on the curve, which occurs just beyond the
termination of the linear-elastic region (Figure 15.2). The stress at this maximum is
the yield strength (sy). Furthermore, tensile strength (TS) corresponds to the stress
 a bowl of wriggling earthworms, see Fig. 5.la. The
he translational motion of the chains past one another. On “wriggling” refers to the translational motion of the chains past one another. On

Crystalline and semi-crystalline states

ndary bonding forces are not strong enough to exert cooling, if the secondary bonding forces are not strong enough to exert
s cannot get straightened out of the tangle to become the themselves, the chains cannot get straightened out of the tangle to become the
ngement of a crystal as in Fig. 5.lb. The translational orderly, parallel arrangement of a crystal as in Fig. 5.lb. The translational
lost during cooling, till the noncrystalline, glassy state is freedom is gradually lost during cooling, till the noncrystalline, glassy state is
y the vibrational degree of freedom remains. The reached, where only the vibrational degree of freedom remains. The
zen in place in the solid in some random configuration “earthworms” are frozen in place in the solid in some random configuration
5.1a. similar to that in Fig. 5.1a.
Crystalline state Molten or glassy state

When primary bonds do not extend in all

directions, one-dimensional chain molecules
or two-dimensional sheet molecules are
formed. Such units have to be aided by
secondary bonding forces to form a three-
dimensional crystal.
(b) (a) (b)
angled up configuration of long chain molecules, (b) the Fig. 5.1 (a) The tangled up configuration of long chain molecules, (b) the
y of the chain molecules characteristic of a crystal. parallel array of the chain molecules characteristic of a crystal.

of the crystalline state is always lower than that of the The free energy of the crystalline state is always lower than that of the
nly when the free energy difference between the two states
noncrystalline state. Only when the free energy difference between the two states
the tendency to crystallize will be strong. Some materials
is large in magnitude, the tendency to crystallize will be strong. Some materials
n network structure of atoms, where there is little free
form a relatively open network structure of atoms, where there is little free

Crystals Viscous polymers

Polymers are semi-crystalline

- Crystalline regions dispersed within the remaining amorphous material.

- Long chains fold and form crystalline part
- A given chain may belong to both crystalline and amorphous regions
- A given crystal consists of more than one chains.
- Chain disorder or misalignment (kinking, twisting, coiling) will lead to
amorphous region.
prene C C C C entirely (up to about 95%) crystalline; in contrast, metal specimens are almost al-

Polymer crystallinity
H H ways entirely crystalline, whereas many ceramics are either totally crystalline or to-
tally noncrystalline. Semicrystalline polymers are, in a sense, analogous to two-phase
metal alloys, discussed previously.
Density and degree The
of crystallinity
density of a crystalline polymer will be greater than an amorphous one of
the same material and molecular weight, since the chains are more closely packed
-Polymer crystallinity is the packing of molecular chains to produce an
together for the crystalline structure. The degree of crystallinity by weight may be
ordered atomic array
determined from accurate density measurements, according to
Figure 14.10 Arrangement
of molecular chains in a
Percent crystallinity unit cell for polyethylene.
(semicrystalline (Adapted from C. W. Bunn, rc 1rs " ra 2
%crystallinity
Chemical Crystallography, ! # 100 (14.8)
polymer)— Oxford University Press, rs 1rc " ra 2
dependence on Oxford, 1945, p. 233.)
specimen density,
where rs is the density of a specimen for which the percent crystallinity is to be de-
and densities of
totally crystalline termined, ra is the density of the totally amorphous polymer, and rc is the density
and totally is the density
of the perfectly crystalline of a specimen
polymer. for which
The values the percent
of ra and rc must crystallinity
be measured is to
bybe determined
amorphous other experimental means. density of the totally amorphous polymer
materials The degree of crystallinity of a polymer depends on the rate of cooling dur-
0.255 nm

ing solidification as well density

as of
onthe
theperfectly crystalline polymer.
chain configuration. During crystallization
upon cooling through the melting temperature, the chains, which are highly ran-
dom and entangled in the viscous liquid, must assume an ordered configuration.
For this to occur, sufficient time must be allowed for the chains to move and
0.741 nm align
0.494 nm
themselves.
The molecular chemistry as well as chain configuration also influence the
C H ability of a polymer to crystallize. Crystallization is not favored in polymers that
are
Arrangement of molecular chains in a composed of chemically complex repeat units (e.g., polyisoprene). On the
unit cell for polyethylene other hand, crystallization is not easily prevented in chemically simple polymers
such as polyethylene and polytetrafluoroethylene, even for very rapid cooling
What are the factors affecting crystallinity in polymers?

• Length of chain: longer chainà amorphous

• Branching of chains: branched chains, cross-linkedà amorphous
• Copolymers: alternating copolymerà crystalline, rest form amorphous
• Tacticity or Stereoisomerism: isotactic and syndiotacticà crystalline,
atacticà amorphous

• Plasticizers: low molecular weight additives added to separate the chains and
prevent crystallization e.g. glycerol, polyethylene glycol
 regions (crystallites), each having a precise alignment, which are interspersed with
ter. The spherulite consists of an aggregate of ribbon-like chain-folded crystallites
Polymer crystals: Lamellae and Spherulites
amorphous regions composed of randomly oriented molecules. The structure of
the crystalline regions may be deduced by examination of polymer single crystals, (lamellae) approximately 10 nm thick that radiate outward from a single nucleation
which may be grown from dilute solutions. These crystals are regularly shaped, thin site in the center. In this electron micrograph, these lamellae appear as thin white lines.
platelets (or lamellae), approximately 10 to 20 nm thick, and on the order of
The detailed structure of a spherulite is illustrated schematically in Figure 14.13.
Spherulites are considered to be the polymer analogue of grains in polycrystalline metals and ceramics
10 !m long. Frequently, these platelets will form a multilayered structure, like that
shown in the electron micrograph of a single crystal of polyethylene, Figure 14.11. Shown here are the individual chain-folded lamellar crystals that are separated by
The molecular chains within each platelet fold back and forth on themselves, with
l folds occurring at the faces; this structure, aptly termed the chain-folded model, is
Direction of Figure 14.13 Schematic
spherulite growth • The spherulite
representation of an consists
of the detailed
Lamellar structure of a spherulite.
.11
ph
chain-folded aggregate of ribbon-like chain-
ene • These crystals are regularly crystallite
folded crystallites (lamellae)
tal. Amorphous
om shaped, thin platelets (or material approximately 10 nm thick that
H.
W. lamellae), approximately 10 radiate outward from a single
nd
ull to 20 nm thick, and on the nucleation site in the center.
wth
order of 10 micrometer long. • individual chain-folded lamellar
of
ral crystals that are separated by
any • platelets will form a Tie molecule

amorphous material.
&
58, multilayered structure
98.]
1496T_c14_489-522 1/10/06 19:23 Page 513
2nd REVISE PAGES
Nucleation Site

1496T_c14_489-522 12/7/05 16:41 Page 514

Interspherulitic
Electron micrograph of a polyethylene single boundary

crystal. 20,000X 14.12 Polymer Crystals • 513514 • Chapter 14 / Polymer Structures

Figure 14.14 A
Figure 14.12 The transmission
photomicrograph
chain-folded (using cross-polarized
structure for a plate-
The chain-folded structure for a plate- ~ 10 nm
shaped polymer
light) showing the
spherulite structure
of polyethylene.
shaped polymer crystallite crystallite. Linear boundaries
form between
adjacent spherulites,
and within each
spherulite appears a
Maltese cross. 525!.
(Courtesy F. P. Price,
General Electric
Company.)

illustrated schematically in Figure 14.12. Each platelet will consist of a number of

molecules; however, the average chain length will be much greater than the thick-
TEM imageamorphous
of spherulite structure of polyethylene
material. Tie-chain molecules that act as connecting links between
adjacent lamellae pass through these amorphous regions.
ness of the platelet.
Callister As the crystallization of a spherulitic structure nears completion, the extremi-
Many bulk polymers that are crystallized from a melt are semicrystalline and ties of adjacent spherulites begin to impinge on one another, forming more or less
 Spherulite in14
natural
Polymerrubber
Structures
Semi-crystalline cellulose
fibres in wood
Chapter

T
Transmission electron micrograph showing the spherulite
ransmission electron micrograph showing the spherulite structure in a natural rubber specimen. Chain-folded lamellar
crystallites approximately 10 nm thick extend in radial directions from the center; they appear as white lines in the micro-

structure inElectrical
a natural rubber specimen. Chain-folded
graph. 30,000!. (Photograph supplied by P. J. Phillips. First published in R. Bartnikas and R. M. Eichhorn, Engineering
Dielectrics, Vol. IIA, Properties of Solid Insulating Materials: Molecular Structure and Electrical Behavior, 1983.

lamellar crystallites approximately 10 nm thick extend in

Copyright ASTM, 1916 Race Street, Philadelphia, PA 19103. Reprinted with permission.)

radial
WHYdirections
STUDY Polymer from the center; they appear as white
Structures?
lines
A relatively large numberin the
of chemical micro-
and structuralgraph.
characteristics affect the properties and behaviors of
2. Degree 30,000X.
of crosslinking—on the stiffness of rubber-
like materials (Section 15.9).
polymeric materials. Some of these influences are as 3. Polymer chemistry—on melting and glass-transition
follows: temperatures (Section 15.14).
1. Degree of crystallinity of semicrystalline polymers—
on density, stiffness, strength, and ductility (Sections
OELASTIC DEFORMATION
Viscoelasticity
An amorphous polymer may behave like a glass at low temperatures, a rubbery
solid at intermediate temperatures [above the glass transition temperature (Section
15.12)], and a viscous liquid as the temperature is further raised. For relatively small
Viscous-liquid+ elastic behaviour
deformations, the mechanical behavior at low temperatures may be elastic; that is,
• in conformity
Found to Hooke’s
in materials which law, E!.anAtapplied
s ! to
respond the highest temperatures,
stress viscous and
by both recoverable or liquid-
permanent deformations, which are
like
timebehavior
dependent prevails. For intermediate temperatures the polymer is a rubbery solid
• that exhibits in
Very common thenon-crystalline
combined mechanical characteristics of these two extremes; the
organic polymers
• condition is termed
Time-dependent viscoelasticity.
permanent deformation is called viscous flow
• In elastic deformation, the rate of strain or strain is not important
Figure 15.4 Schematic tensile
Amorphouscurve
stress–strain material:
for a
- Glass at low polymer.
semicrystalline temperatures: not all molecular motion is frozen
Specimen
- Rubbery
contours solid above
at several glass
stages of transition temperature: conformational
changes
deformation are included. (From
- Viscous liquid at high temperature: segments between
Stress

Jerold M. Schultz, Polymer Materials

entanglements can recover
Science, copyright © 1974, p. 488.
Reprinted by permission of Prentice
• At low temperature: elastic (Hooke’s law)
Hall, Inc., Englewood Cliffs, NJ.)
• At high temperature: viscous liquid-like behaviour
• At intermediate temperatures: combined mechanical characteristics:
Viscoelasticity

Strain
 Strain rate in viscoelastic materials
528 • Chapter 15 / Characteristics, Applications, and Processing of Polymers
• Strain shows no dependence on time
Elastic Elastic (strain rate is 0)
Figure 15.5 • Instantaneous strain on application of
(a) Load versus load
time, where load

Strain
is applied Load
instantaneously at
time ta and released
ta Time tr ta Time tr
at tr. For the
load–time cycle in (a) (b)
(a), the strain-versus- Viscoelastic Viscous
time responses are
for totally elastic
(b), viscoelastic
- Instantaneous elastic
Strain

Strain
(c), andbyviscous
strain followed a - Delayed strain with time
viscous, (d) behaviors.
time-dependent - Deformation is not reversible
strain

ta Time tr ta Time tr
(c) (d)
 Fibers
• Polymers are capable of being drawn into long filaments having at least a 100:1 length-
to-diameter ratio.
• All the chains are more or less aligned in the long direction of the fibre
• High elastic modulus: Their strength and elastic modulus in a direction parallel to the
fibre length are an order of magnitude larger as compared to the nonaligned structure.
• High degree of crystallinity leads to high tensile strength: linear and unbranched
polymer chains, polar groups increase inter-chain intermolecular forces
• Examples: Nylon– polyamide fiber

110 Structure of Solids

CH2 N CH2 CH2 CH2 C

CH2 C CH2 CH2 CH2 N

O H

Hydrogen bond
H O

CH2 N CH2 CH2 CH2 C

C CH2 CH2 CH2 N CH2

 Elastomers
Rubber-like elasticity

• Materials which undergo recoverable deformation of a few hundred per cent are called elastomers and exhibit
rubber-like elasticity.
• The stress is not proportional to strain in these materials, in contrast to ordinary elastic materials.
• Long chain polymers with some cross-linking between the chains.
• This feature is what keeps the molecules from slipping past one another permanently during stretching
• After cross-linking, the translational motion of chains gets restricted to segmental mobility between cross-
linking points. When a stress is applied to an elastomer, equilibrium in the molecular configuration is
established fairly quickly so that we can ignore the time dependent aspects of stretching as a first
approximation.
• Do not easily crystallize
• Amorphous
• Onset of plastic deformation is delayed: restricting the motions of chains
erial shrinks to re- 1496T_c15_523-576 12/8/05 14:57 Page 543
transition temperature, an elastomer becomes brittle such that its stress–strain
deformation, which Photograph showing (from top to bottom) an
kle-free, transparent
behavior resembles curve A in Figure 15.1.
electrical connection, a piece of as-received polymer
Ds and many other

Elastomers
shrink-tubing, and the constricted tubing around the
Vulcanization
packaged in shrink- junction—application of heat to the tubing caused its
vulcanization
diameter The crosslinking
to shrink. (Photography in elastomers is called vulcanization, which is achieved by
by S. Tanner.) process
Vulcanization:
a nonreversible chemical reaction, ordinarily carried outcrosslinking process
at an elevated tempera- in elastomers 15.9 Deformation
Stress-strain curve ture. In Processes
Relaxation most vulcanizing
249 reactions, sulfur compounds are added to the heated
elastomer; chains of sulfur atoms bond with adjacent polymer backbone chains 10 F
OF ELASTOMERS and crosslink them, which is accomplished according to the following reaction:60
S
6
e fascinating properties of the elastomeric materials is their rubber-like elas-
H CH3 H H H CH3 H H 8 u
t is, they have the ability to be deformed to quite large deformations, and 50 v
0.8
ically spring back to their original form. This results from crosslinks
C inCtheC C C C C C r

Stress (103 psi)

hat provide a force to restore the chains to their undeformed conforma- 6

Stress (MPa)
40
stomeric behavior0.6 was probably first observed in natural rubber;Hhowever, H H H
Stress, MN m–2

ew years have brought about the synthesis of a large number of elastomers

# (m # n) S (S)m (S)n 30(15.4) Vulcanized
de variety of properties. Typical stress–strain characteristics of elastomeric 4
in Figure 15.1, curve C. Their moduli of elasticityHare quite
are displayed 0.4 H H H 20
, furthermore, vary with strain since the stress–strain curve is nonlinear.
n unstressed state, an elastomer will be amorphous and composed C C ofC C C C C C 2
10
ed molecular chains
0.2 that are highly twisted, kinked, and coiled. Elastic de- Unvulcanized
H CHun-
n, upon application of a tensile load, is simply the partial uncoiling, 3 H H H CH3 H H
0 0
and straightening, and the resultant elongation of the chains in the stress
in which the two crosslinks shown consist of m and n sulfur atoms. Crosslink 0main 1 2 3 4 5 6
a phenomenon represented in Figure 15.15. Upon chainrelease
sites of
arethecarbon
stress, atoms that were doubly bonded before vulcanization but, Strain
0 200 400
after vulcanization, have become singly bonded.
% Strain Unvulcanized rubber, which contains very few crosslinks, is soft and tacky
ntation of
Fig.
ules (a) 10.5
in The stress-strain curve for an and has poor resistance to• abrasion.
elastomer.
Crosslinks Sulfur Modulus of elasticity,
compounds tensile to
are added strength,
the andStress–strain
crosslinks.
heated curves for
elastomer; vulcanized
chains and unvulcan
of sulfur
resistance to degradation by oxidation are all enhanced by vulcanization.presented
The mag-in Figure 15.16. To produce a rubber that is capa
ng elastic
n applied
atoms bond with adjacent polymer
nitude of the modulus of elasticity is directly proportional to the density without backbone chainschain
rupture of the primary
of the
andbonds,
crosslink
there must be r
rom Z. D. ! them ! Polymers: Rubber and these must be widely separated. Useful rubbers result w
operties of ANELASTIC BEHAVIOUR • Unvulcanized rubber, which contains (by weight) of sulfur are added to 100 parts of rubber. Thi
very few crosslinks, is soft and
d edition. one crosslink for every 10 to 20 repeat units. Increasing the
y & Sons,
(b)
has poor resistance to abrasion. hardens the rubber and also reduces its extensibility.Also, sin
deformation
n of John that occurs as a function of time is called anelastic • Elastic modulus increases with increasing temperature.
elastomeric materials are thermosetting in nature.
Sons, Inc.)
The elastic deformation of During elasticcontinues
the material deformation
even after the • Magnitude of elastic modulus ∝ density of cross-links.
the load, due to some relaxation process within the material. On
(a) Concept Check 15.5
Unstressed
e load, some part of state
the elastic deformation is recovered only as a
 configurations and hence lowers the configurational entropy. In the
en the molecules are all fully stretched out, the possible configuration is
and the configurational entropy is zero, recall Eq. (2.5). When a
Driving force for elastic deformation in elastomer is entropy
rubber is heated, the increase in thermal energy tends to coil back the
molecules against the stretching force.
Thermodynamics
coiling and uncoiling of a long chain molecule in an elastomer is
cally illustrated in Fig. 10.4. Note that full stretching out does not mean

Increase tensile stress A new definition of entropy

S =k log W

Increase temperature

High entropy Low entropy

Ludwig Boltzmann
The coiling and uncoiling of an elastomer chain molecule as a function
of tensile stress and temperature. W= number of ways of arrangement of molecules
The stretching process merely uncoils the S= Entropy is a measure of the possible number of ways in
in the C–C bond angle of 109.5° along the backbone of the chain. If
coiledthemolecules, butenergy)
doesofnot change wouldthe also which the energy of the system can be distributed among
to happen, enthalpy (bond the elastomer
bondto lengths
n addition or bond entropy.
the configurational angles.Experimental
This behaviourresults is
indicate the molecules.
changeinin contrast to onwhat
the enthalpy happens
stretching a rubberinis an
zero.ordinary
The stretching
merelyelastic
uncoilsmaterial,
the coiledwhere bond
molecules, butlengths
does notare clearly
change the bond
changed
r bond angles. This behaviour is in contrast to what happens in an Some interesting reads: “Anxiety and Equation” by Eric Johnson
elastic material, where bond lengths are clearly changed, see Fig. 10.1. “Entropy Demystified” by A. Ben Naim
 Food for thought..

Why does gas in a container expand spontaneously? Why does a hot coffee mug get cold spontaneously on
keeping for sometime?

Why does not the gas contract on its own If you keep a cold coffee mug on table, why doesn’t it get
spontaneously? hot on its own spontaneously?

Dispersal of energy (distribution of energy)à spontaneityà entropy

The statistical or molecular definition of Entropy…
Liquid state
Molten viscous state

Solid crystalline state

On a ”random” lecture day

De
cre
asi When students prefer to choose
ng their company..
En
tr op
y
On “exam” day:
Perfectly ordered arrangement
 configurations and hence lowers the configurational entropy. In the
S = k ln W
en the molecules are all fully stretched out, the possible configuration is
Driving force for elastic deformation is entropy
and the configurational entropy is zero, recall Eq. (2.5). When a
rubber is heated, the increase in thermal energy tends to coil back the
S = k ln W
molecules against the stretching force.
coiling and uncoiling of a long chain molecule in an elastomer is
cally illustrated in Fig. 10.4. Note that full stretching out does not mean

Google images

Increase tensile stress

Diffusion in materials
Increase temperature Pressure
Stretchability
High entropy Low entropy Molecular driving forces by Dill and Bromberg
The coiling and uncoiling of an elastomer chain molecule as a function
of tensile stress and temperature.

Diffusion in materials
in the C–C bond angle of 109.5° along the backbone of the chain. If
to happen, the enthalpy (bond energy) of the elastomer would also Stretchability in rubber
n addition to the configurational entropy. Experimental results indicate
change in the enthalpy on stretching a rubber is zero. The stretching Which state will have higher entropy?
merely uncoils the coiled molecules, but does not change the bondStretchability of rubber
r bond angles. This behaviour is in contrast to what happens in an
s by Dill and Bromberg Book: Molecular driving forces, Dill and Bromberg
elastic material, where bond lengths are clearly changed, see Fig. 10.1.