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Bonding:

-- Mostly ionic, some covalent.


-- % ionic character increases with difference in
electronegativity.
Large vs small ionic bond character:

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University.

Frenkel Defect
Shottky Defect

Shottky
Defect:

Frenkel
Defect

Adapted from Fig. 12.21, Callister


7e. (Fig. 12.21 is from W.G.
Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)

Equilibrium concentration of defects

Ex: NaCl

Na +

Cl cation
vacancy

Substitutional cation impurity


Ca 2+
Na +
Na +
initial geometry

Ca 2+ impurity

Substitutional anion impurity


O2-

initial geometry

Cl Cl O2- impurity

Ca 2+
resulting geometry
an ion vacancy

resulting geometry

MgO-Al2O3 diagram:

Adapted from Fig.


12.25, Callister 7e.

Room T behavior is usually elastic, with brittle failure.


3-Point Bend Testing often used.
--tensile tests are difficult for brittle materials.
cross section

d
b

rect.

R
circ.

L/2

L/2

Adapted from Fig. 12.32,


Callister 7e.

d = midpoint
deflection

3-point bend test to measure room T strength.


cross section

d
b

rect.

L/2

L/2

Adapted from Fig. 12.32,


Callister 7e.

d = midpoint
deflection

circ.
location of max tension

Typ. values:
fs
! (MPa) E(GPa)
Si nitride
250-1000 304
Si carbide
100-820 345
Al oxide
275-700 393
glass (soda)
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Material

Data from Table 12.5, Callister 7e.

Poly

mer

many

repeat unit
repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Polyvinyl chloride (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 7e.

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Molecular weight, Mi: Mass of a mole of chains.

Lower M

higher M

Mw is more sensitive to higher


molecular weights
Adapted from Fig. 14.4, Callister 7e.

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Covalent chain configurations and strength:

secondary

bonding

Linear

B ranched

Cross-Linked

Network

Adapted from Fig. 14.7, Callister 7e.

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Tacticity stereoregularity of chain

H H H H H H H H
C C C C C C C C
H R H R H R H R
H H H R H H H R
C C C C C C C C
H R H H H R H H
H H H H H R H H
C C C C C C C C
H R H R H H H R
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CH3

H
C C

CH2

CH2

CH3

C C

CH2

CH2
H

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

bulky groups on same side of


chain

bulky groups on opposite sides


of chain

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Adapted from Fig.


14.9, Callister 7e.

random

alternating
block

graft
15

Adapted from Fig.


14.6, Callister 7e.

16

Adapted from Fig.


14.10, Callister 7e.

Ex: polyethylene unit cell


Crystals must contain the polymer
chains in some way
Chain folded structure

Adapted from Fig.


14.12, Callister 7e.

10 nm

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Polymers rarely 100% crystalline


Too difficult to get all those chains aligned
crystalline
region
% Crystallinity: % of material
that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
amorphous
region
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.)

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What factors affect Tm and Tg?

Adapted from Fig. 15.18,


Callister 7e.

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i.e. stress-strain behavior of polymers

FS of polymer ca. 10% that of metals

elastic modulus
less than metal

Strains deformations > 1000% possible


(for metals, maximum strain ca. 10% or less)

Adapted from Fig. 15.1,


Callister 7e.

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Near Failure

fibrillar
structure

!(MPa)

x brittle failure
onset of
necking

near
failure

plastic failure

x
Initial
unload/reload

!
aligned, networked
crosscase
linked
case

crystalline
regions
slide
semicrystalline
case

amorphous
regions
elongate

crystalline
regions align

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, Prentice21
Hall, Inc., 1974, pp. 500-501.)

!(MPa)
x brittle failure

plastic failure

elastomer

!
initial: amorphous chains are
kinked, cross-linked.

final: chains
are straight,
still
cross-linked

Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
curve (green) adapted
from Fig. 15.15, Callister
7e. (Fig. 15.15 is from
Z.D. Jastrzebski, The
Nature and Properties of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1987.)

Deformation
is reversible!

Compare to responses of other polymers:


-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
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Thermoplastics:
-- little crosslinking
-- ductile
-- soften w/heating
-- polyethylene
polypropylene
polycarbonate
polystyrene

T
viscous
liquid

mobile
liquid

crystalline
solid
Thermosets:
-- large crosslinking
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin

Callister,
rubber
Fig. 16.9!

tough
plastic

Tm
Tg

partially
crystalline
solid

Molecular weight
Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer,
Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc.,
1984.)

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Decreasing T...
-- increases E
-- increases TS
-- decreases %EL
Increasing
strain rate...
-- same effects
as decreasing T.

!(MPa)
80 4C
60

20C

40

Data for the


semicrystalline
polymer: PMMA
(Plexiglas)

40C

20
0

60C
0

0.1

0.2

to 1.3
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.)

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