Mechanical Behavior mostly

Ceramics, Glasses and Polymers

Chapter 6: Part 2
Dr. R. Lindeke
 Measuring Elastic Modulus
• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing is often used.
-- tensile tests are difficult for brittle materials!
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b  = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F F L3 F L3
x E= =
F  4bd 3  12 p R 4
slope =
 rect. circ.
cross cross
 section section
linear-elastic behavior
 Measuring Strength
• 3-point bend test to measure room T strength.
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b  = midpoint
rect. circ.
deflection
location of max tension

• Flexural strength: • Typ. values:

Material sfs (MPa) E(GPa)
1.5Ff L Ff L
s fs = = Si nitride 250-1000 304
bd 2 pR3 Si carbide 100-820 345
F rect. Al oxide 275-700 393
Ff x glass (soda) 69 69
Data from Table 12.5, Callister 7e.


fs
 Mechanical Issues:
• Properties are significantly dependent on processing
– and as it relates to the level of Porosity:
• E = E0(1-1.9P+0.9P2) – where P is a fraction ‘porosity’
• sfs = s0e-nP -- s0 & n are empirical values and functions of porosity

• Because the very unpredictable nature of ceramic

defects, we do not simply add a factor of safety for
tensile loading
• We may add compressive surface loads
• We often choose to avoid tensile loading at all – most ceramic
loading of any significance is compressive (consider buildings,
dams, brigdes and roads!)
 Figure 6.15 Stress (σm) at the tip of a Griffith crack.

• Where the so called

Griffith cracks are
introduced into the
ceramic or glass
materials during
processing
• The crack tip “stress
concentration” sm can
be very high since the
“radius” of the crack
tip () can be on the
order of ionic
diameters!
 Mechanical Properties
• i.e. stress-strain behavior of polymers

brittle polymer

sFS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

Adapted from Fig. 15.1,

Strains – deformations > 1000% possible Callister 7e.

(for metals, maximum strain ca. 100% or less)

 Tensile Response: Brittle & Plastic
Near Failure s(MPa) fibrillar
structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

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 7e.
-- decreases ductility (%EL) (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
s(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!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
 Thermoplastics vs. Thermosets
T
• Thermoplastics: Callister,
-- little crosslinking viscous rubber
Fig. 16.9
mobile liquid Tm
-- ductile tough
liquid
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

• Thermosets: Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer, Jr.,
-- large crosslinking Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
 T and Strain Rate: Thermoplastics

• Decreasing T...
s(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

• Chain stiffness increased by

1. Bulky sidegroups
2. Polar groups or sidegroups
3. Double bonds or aromatic
chain groups

• Regularity (tacticity) – affects Tm

only

Adapted from Fig. 15.18,

Callister 7e.
Figure 6.40 Typical thermal-expansion measurement of an
inorganic glass or an organic polymer indicates a glass transition
temperature, Tg, and a softening temperature, Ts .
 Time Dependent Deformation
• Stress relaxation test: • Data: Large drop in Er
-- strain to eo and hold. for T > Tg. (amorphous
5 polystyrene)
-- observe decrease in 10 rigid solid
Er (10s) (small relax) Adapted from Fig.
stress with time. in MPa 10
3
15.7, Callister 7e. (Fig.
transition 15.7 is from A.V.
1
tensile test 10 region Tobolsky, Properties
and Structures of
eo strain 10 -1
Polymers, John Wiley
and Sons, Inc., 1960.)
viscous liquid
s(t) 10 -3 (large relax)
60 100 140 180 T(°C)
time Tg
• Relaxation modulus: • Sample Tg(C) values:
s(t ) PE (low density) - 110
E r (t ) = PE (high density) - 90
eo PVC + 87
Selected values from
Table 15.2, Callister 7e.
PS +100
PC +150
Figure 6.41 Upon heating, a crystal
undergoes modest thermal expansion
up to its melting point (Tm), at which a
sharp increase in specific volume
occurs. Upon further heating, the
liquid undergoes a greater thermal
expansion. Slow cooling of the liquid
would allow crystallization abruptly at
Tm and a retracing of the melting plot.
Rapid cooling of the liquid can
suppress crystallization producing a
supercooled liquid. In the vicinity of
the glass transition temperature (Tg),
gradual solidification occurs. A true
glass is a rigid solid with thermal
expansion similar to the crystal, but
an atomic-scale structure similar to
the liquid (see Figure 4.21).
Figure 6.42 Illustration of terms used to define
viscosity, η, in Equation 6.19.
Figure 6.43 Viscosity of a
typical soda–lime–silica
glass from room
temperature to 1,500°C.
Above the glass transition
temperature (~450°C in
this case), the viscosity
decreases in the Arrhenius
fashion (see Equation
6.20).
Figure 6.44 Thermal
and stress profiles
occurring during the
production of
tempered glass. The
high breaking
strength of this
product is due to the
residual compressive
stress at the material
surfaces.
Figure 6.45 Modulus of
elasticity as a function of
temperature for a typical
thermoplastic polymer with 50%
crystallinity. There are four
distinct regions of viscoelastic
behavior: (1) rigid, (2) leathery,
(3) rubbery, and (4) viscous.
 Figure 6.46 In comparison
with the plot of Figure 6.45,
the behavior of the
completely amorphous and
completely crystalline
thermoplastics falls below
and above that for the 50%
crystalline material. The
completely crystalline
material is similar to a metal
or ceramic in remaining rigid
up to its melting point.
Figure 6.47 Cross-linking produces a network structure by the formation of
primary bonds between adjacent linear molecules. The classic example shown
here is the vulcanization of rubber. Sulfur atoms form primary bonds with
adjacent polyisoprene mers, which is possible because the polyisoprene chain
molecule still contains double bonds after polymerization. [It should be noted
that sulfur atoms can themselves bond together to form a molecule chain.
Sometimes, cross-linking occurs by an (S)n chain, where n > 1.]
Figure 6.48 Increased cross-linking of a thermoplastic
polymer produces increased rigidity of the material.
Figure 6.49 The modulus of elasticity versus
temperature plot of an elastomer has a pronounced
rubbery region.
Figure 6.50 Schematic illustration of the uncoiling of (a) an
initially coiled linear molecule under (b) the effect of an external
stress. This illustration indicates the molecular-scale mechanism
for the stress versus strain behavior of an elastomer, as shown in
Figure 6.51.
Figure 6.51 The stress–
strain curve for an elastomer
is an example of nonlinear
elasticity. The initial low-
modulus (i.e., low-slope)
region corresponds to the
uncoiling of molecules
(overcoming weak,
secondary bonds), as
illustrated by Figure 6.50.
The high-modulus region
corresponds to elongation of
extended molecules
(stretching primary, covalent
bonds), as shown by Figure
6.50b. Elastomeric
deformation exhibits
hysteresis; that is, the plots
during loading and
unloading do not coincide.
Figure 6.52 Modulus of elasticity versus temperature for a variety of
common polymers. The dynamic elastic modulus in this case was measured in
a torsional pendulum (a shear mode). The DTUL is the deflection temperature
under load, the load being 264 psi. This parameter is frequently associated
with the glass transition temperature.

(From
Modern
Plastics
Encyclope
dia, 1981–
82, Vol. 58,
No. 10A,
McGraw-
Hill Book
Company,
New York,
October
1981.)