Polymer: Structure and Properties: Anshul Gautampurkar
Polymer: Structure and Properties: Anshul Gautampurkar
Polymer: Structure and Properties: Anshul Gautampurkar
properties
Anshul Gautampurkar
15POL2004
(2015-2017)
R●
Odd + even = odd: unpaired electron survives
Addition polymerization has three steps
secondary
bonding
Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H
A A
C C
E E
B D D B
mirror plane
Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R
H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
H R H H H R H H
H H H H H R H H
atactic – R groups random C C C C C C C C
H R H R H H H R
cis/trans Isomerism
cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same side of bulky groups on opposite sides
chain of chain
Copolymers Adapted from Fig.
14.9, Callister 7e.
A– B–
graft
Polymer Crystallinity
Adapted from Fig.
14.10, Callister 7e.
brittle polymer
plastic
elastomer
elastic modulus
– less than metal
e
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from Figs. 15.12
& 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, Prentice-Hall, Inc., 1974, pp.
500-501.)
Predeformation by Drawing
• Drawing…(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the stretching direction
• Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction Adapted from Fig. 15.13, Callister
-- decreases ductility (%EL) 7e. (Fig. 15.13 is from J.M. Schultz,
Polymer Materials Science, Prentice-
• Annealing after drawing... Hall, Inc., 1974, pp. 500-501.)
-- decreases alignment
-- reverses effects of drawing.
• Comparable to cold working in metals!
Tensile Response: Elastomer Case
(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset figures
along elastomer curve
(green) adapted from Fig.
15.15, Callister 7e. (Fig.
plastic failure
x 15.15 is from Z.D.
Jastrzebski, The Nature
and Properties of
x Engineering Materials, 3rd
elastomer ed., John Wiley and Sons,
1987.)
final: chains
e are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!
• Decreasing T...
(MPa)
-- increases E 80 4°C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20°C (Plexiglas)
• Increasing 40 40°C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60°C
0
0 0.1 0.2 e 0.3
Adapted from Fig. 15.3, Callister 7e. (Fig. 15.3 is from T.S. Carswell and J.K.
Nason, 'Effect of Environmental Conditions on the Mechanical Properties of
Organic Plastics", Symposium on Plastics, American Society for Testing and
Materials, Philadelphia, PA, 1944.)
Melting vs. Glass Transition Temp.
What factors affect Tm and
Tg?
Both Tm and Tg increase with
increasing chain stiffness
alligned chains
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(c)atactic.
nonsymmetrical
Figure 15.9 Three
(b)syndiotactic, and
monomers: (a) isotactic,
possible arrangements of
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under
license.
Figure 15.10 Four types of copolymers: (a) alternating monomers, (b) random monomers, (c)
block copolymers, and (d) grafted copolymers. Circles of different colors or sizes represent
different monomers.
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Figure 15.11
Copolymerization
produces the polymer
ABS, which is really
made up of two
copolymers, SAN and
BS, grafted together.
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Section 15.7 Effect of
Temperature on Thermoplastics
Degradation temperature - The temperature above which a polymer
burns, chars, or decomposes.
Glass temperature - The temperature range below which the amorphous
polymer assumes a rigid glassy structure.
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48
behavior of
thermoplastics.
Figure 15.12 The
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
Figure 15.15 The folded chain ,model for crystallinity in polymers, shown
in (a) two dimensions and (b) three dimensions.
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Figure 15.16 Photograph of spherulitic
crystals in an amorphous matrix of nylon (
200). (From R. Brick, A. Pense and R.
Gordon, Structure and Properties of
Engineering Materials, 4th Ed., McGraw-Hill,
1977.)
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Polymer Structure I
amorphous semi-crystalline
polymer polymer
Shish-kebab morphology
Similarly, a linear polymer can pack well, whereas a branched isomer cannot
stretch
leave
ENTROPY WORK!
Polymer Structure IX
Plastics
Fall between the elastomers and fibers. However there is no exact boundary
Harder to stretch than elastomers (Because of crystalline regions?). But preserve
their shape when stretched unlike elastomers (Strain induced crystallization, stiff
chains)
They are pliable, that is, they can be shaped and molded easily
Thermoplastics: Melt when heated and can be melted again after cooling
Thermosets: Undergoes crosslinking when heated, so does not melt again,
decomposes if heated further
Flexible plastics: Plastics above their Tg. Flexible, soft
Rigid plastics: Plastics below their glass transition temperature (Tg). Brittle, hard
• Different polymers have different segments on their backbones. The ease of movement of these
segments (portions of the chain) depends on the structure, physical environment of the chain etc.
of the segment.
• Any movement of these segments require energy which is kinetic in this case, right? Then each
different polymer would have different energy requirement for the movement of these segments
(different polymer = different structure, different physical environment of the chain etc).
• Below glass transition temperature, these segments do not have sufficient energy to move. So, if
you apply some stress, say if you try to bend a polymer which is below its Tg then the segments
won’t be able to move into new positions to relieve the stress which you have placed on them;
which will make the polymer brittle. Above Tg they would, so they would be flexible.
• So it should now be obvious that elastomers are elastomers above their Tg. Below, they are not
elastomers, they are glassy, because they are not flexible anymore (Remember my experiment
with rubber glove and liquid nitrogen during the lecture).
Polymer Structure XI
Melting
• Melting is a transition which occurs in crystalline polymers.
• Melting happens when the polymer chains fall out of their crystal structures, and become a
disordered liquid.
Crosslinking
with sulphur
(vulcanization)
Synthetic rubber