Chapter 7 / Mechanical Properties

7.12 INFLUENCE OF POROSITY ON THE MECHANICAL

PROPERTIES OF CERAMICS
For some ceramic fabrication techniques (Sections 14.8 and 14.9), the precursor
material is in the form of a powder. Subsequent to compaction or forming of these
powder particles into the desired shape, pores or void spaces will exist between
the powder particles. During the ensuing heat treatment, much of this porosity will
be eliminated; however, it is often the case that this pore elimination process is
incomplete and some residual porosity will remain (Figure 14.25). Any residual
porosity will have a deleterious influence on both the elastic properties and strength.
For example, it has been observed for some ceramic materials that the magnitude
of the modulus of elasticity E decreases with volume fraction porosity P according to

E ⫽ E0(1 ⫺ 1.9P ⫹ 0.9P2) (7.21)

where E0 is the modulus of elasticity of the nonporous material. The influence of

volume fraction porosity on the modulus of elasticity for aluminum oxide is shown
in Figure 7.20; the curve represented in the figure is according to Equation 7.21.
Porosity is deleterious to the flexural strength for two reasons: (1) pores reduce
the cross-sectional area across which a load is applied, and (2) they also act as
stress concentrators—for an isolated spherical pore, an applied tensile stress is
amplified by a factor of 2. The influence of porosity on strength is rather dramatic;
for example, it is not uncommon that 10 vol% porosity will decrease the flexural
strength by 50% from the measured value for the nonporous material. The degree
of the influence of pore volume on flexural strength is demonstrated in Figure 7.21,
again for aluminum oxide. Experimentally it has been shown that the flexural
strength decreases exponentially with volume fraction porosity (P) as

␴fs ⫽ ␴0 exp(⫺nP) (7.22)

In this expression ␴0 and n are experimental constants.

7.15 VISCOELASTICITY
An amorphous polymer may behave like a glass at low temperatures, a rubbery
solid at intermediate temperatures [above the glass transition temperature (Section
11.15)], and a viscous liquid as the temperature is further raised. For relatively
small deformations, the mechanical behavior at low temperatures may be elastic;
that is, in conformity to Hooke’s law, ␴ ⫽ E⑀. At the highest temperatures, viscous
or liquidlike behavior prevails. For intermediate temperatures is found a rubbery

S-22
 7.15 Viscoelasticity ● S-23

60
400

50

Modulus of elasticity (106 psi)

Modulus of elasticity (GPa)
300
40

200 30

20
100
10

0 0
0.0 0.2 0.4 0.6 0.8 1.0
Volume fraction porosity

FIGURE 7.20 The influence of porosity on the modulus of elasticity for

aluminum oxide at room temperature. The curve drawn is according to Equation
7.21. (From R. L. Coble and W. D. Kingery, ‘‘Effect of Porosity on Physical
Properties of Sintered Alumina,’’ J. Am. Ceram. Soc., 39, 11, Nov. 1956, p. 381.
Reprinted by permission of the American Ceramic Society.)

solid that exhibits the combined mechanical characteristics of these two extremes;
the condition is termed viscoelasticity.
Elastic deformation is instantaneous, which means that total deformation (or
strain) occurs the instant the stress is applied or released (i.e., the strain is indepen-
dent of time). In addition, upon release of the external stress, the deformation is
totally recovered—the specimen assumes its original dimensions. This behavior is

40

250
Flexural strength (103 psi)

200 30
Flexural strength (MPa)

150
20

100

10
50

0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Volume fraction porosity

FIGURE 7.21 The influence of porosity on the flexural strength for aluminum
oxide at room temperature. (From R. L. Coble and W. D. Kingery, ‘‘Effect of
Porosity on Physical Properties of Sintered Alumina,’’ J. Am. Ceram. Soc., 39,
11, Nov. 1956, p. 382. Reprinted by permission of the American Ceramic
Society.)
S-24 ● Chapter 7 / Mechanical Properties

FIGURE 7.26 (a) Load

versus time, where

Strain
load is applied

Load
instantaneously at time
ta and released at tr .
For the load–time cycle
ta Time tr ta Time tr
in (a), the strain-
(a) (b) versus-time responses
are for totally elastic
(b), viscoelastic (c), and
viscous (d ) behavior.
Strain

Strain
ta Time tr ta Time tr
(c) (d)

represented in Figure 7.26b as strain versus time for the instantaneous load–time
curve, shown in Figure 7.26a.
By way of contrast, for totally viscous behavior, deformation or strain is not
instantaneous; that is, in response to an applied stress, deformation is delayed or
dependent on time. Also, this deformation is not reversible or completely recovered
after the stress is released. This phenomenon is demonstrated in Figure 7.26d.
For the intermediate viscoelastic behavior, the imposition of a stress in the
manner of Figure 7.26a results in an instantaneous elastic strain, which is followed
by a viscous, time-dependent strain, a form of anelasticity (Section 7.4); this behavior
is illustrated in Figure 7.26c.
A familiar example of these viscoelastic extremes is found in a silicone polymer
that is sold as a novelty and known by some as ‘‘silly putty.’’ When rolled into a
ball and dropped onto a horizontal surface, it bounces elastically—the rate of
deformation during the bounce is very rapid. On the other hand, if pulled in tension
with a gradually increasing applied stress, the material elongates or flows like a
highly viscous liquid. For this and other viscoelastic materials, the rate of strain
determines whether the deformation is elastic or viscous.

VISCOELASTIC RELAXATION MODULUS

The viscoelastic behavior of polymeric materials is dependent on both time and
temperature; several experimental techniques may be used to measure and quantify
this behavior. Stress relaxation measurements represent one possibility. With these
tests, a specimen is initially strained rapidly in tension to a predetermined and
relatively low strain level. The stress necessary to maintain this strain is measured
as a function of time, while temperature is held constant. Stress is found to decrease
with time due to molecular relaxation processes that take place within the polymer.
We may define a relaxation modulus Er (t), a time-dependent elastic modulus for
viscoelastic polymers, as

␴ (t)
Er (t) ⫽ (7.23)
⑀0
 7.15 Viscoelasticity ● S-25

FIGURE 7.27 Schematic plot of logarithm of

relaxation modulus versus logarithm of time
T1
for a viscoelastic polymer; isothermal curves
are generated at temperatures T1 through T7 .
The temperature dependence of the
relaxation modulus is represented as log
Er (t1) versus temperature.
Log relaxation modulus, Er(t)

T2
T3

T7 > T6 > . . . > T1

T4

T5
T6

T7

t1

Log time, t

where ␴ (t) is the measured time-dependent stress and ⑀0 is the strain level, which
is maintained constant.
Furthermore, the magnitude of the relaxation modulus is a function of tempera-
ture; and to more fully characterize the viscoelastic behavior of a polymer, isother-
mal stress relaxation measurements must be conducted over a range of temperatures.
Figure 7.27 is a schematic log Er (t)-versus-log time plot for a polymer that exhibits
viscoelastic behavior; included are several curves generated at a variety of tempera-
tures. Worth noting from this figure are (1) the decrease of Er (t) with time (corre-
sponding to the decay of stress, Equation 7.23), and (2) the displacement of the
curves to lower Er (t) levels with increasing temperature.
To represent the influence of temperature, data points are taken at a specific
time from the log Er (t)-versus-log time plot—for example, t1 in Figure 7.27—and
then cross-plotted as log Er (t1) versus temperature. Figure 7.28 is such a plot for
an amorphous (atactic) polystyrene; in this case, t1 was arbitrarily taken 10 s after
the load application. Several distinct regions may be noted on the curve shown in
this figure. For the first, at the lowest temperatures, in the glassy region, the material
is rigid and brittle, and the value of Er (10) is that of the elastic modulus, which
initially is virtually independent of temperature. Over this temperature range, the
strain–time characteristics are as represented in Figure 7.26b. On a molecular level,
the long molecular chains are essentially frozen in position at these temperatures.
As the temperature is increased, Er (10) drops abruptly by about a factor of
103 within a 20⬚C (35⬚F) temperature span; this is sometimes called the leathery,
or glass transition region, and the glass transition temperature (Tg , Section 11.16)
lies near the upper temperature extremity; for polystyrene (Figure 7.28), Tg ⫽ 100⬚C
(212⬚F). Within this temperature region, a polymer specimen will be leathery; that
S-26 ● Chapter 7 / Mechanical Properties

Temperature (°F) FIGURE 7.28 Logarithm

5 160 200 240 280 320 360 of the relaxation modulus
10
107 versus temperature for
amorphous polystyrene,
104 showing the five different
106
regions of viscoelastic
Glassy behavior. (From A. V.
103
105 Tobolsky, Properties and
Structures of Polymers.
Relaxation modulus, Er(10) (MPa)

102 Copyright  1960 by

104
John Wiley & Sons, New

Relaxation modulus (psi)

Leathery
York. Reprinted by
10 permission of John
103
Wiley & Sons, Inc.)
1
102
Rubbery

10⫺1
Rubbery flow 10

10⫺2
1

Viscous flow (liquid)

10⫺3
10–1

10⫺4
60 80 100 120 140 160 180 200
Temperature (°C)
Tg Tm

is, deformation will be time dependent and not totally recoverable on release of
an applied load, characteristics depicted in Figure 7.26c.
Within the rubbery plateau temperature region (Figure 7.28), the material
deforms in a rubbery manner; here, both elastic and viscous components are present,
and deformation is easy to produce because the relaxation modulus is relatively low.
The final two high-temperature regions are rubbery flow and viscous flow. Upon
heating through these temperatures, the material experiences a gradual transition
to a soft rubbery state, and finally to a viscous liquid. Within the viscous flow region,
the modulus decreases dramatically with increasing temperature; and, again, the
strain–time behavior is as represented in Figure 7.26d. From a molecular standpoint,
chain motion intensifies so greatly that for viscous flow, the chain segments experi-
ence vibration and rotational motion quite independently of one another. At these
temperatures, any deformation is entirely viscous.
Normally, the deformation behavior of a viscous polymer is specified in terms
of viscosity, a measure of a material’s resistance to flow by shear forces. Viscosity
is discussed for the inorganic glasses in Section 8.16.
The rate of stress application also influences the viscoelastic characteristics.
Increasing the loading rate has the same influence as lowering temperature.
The log Er (10)-versus-temperature behavior for polystyrene materials having
several molecular configurations is plotted in Figure 7.29. The curve for the amor-
phous material (curve C ) is the same as in Figure 7.28. For a lightly crosslinked
atactic polystyrene (curve B), the rubbery region forms a plateau that extends to
 7.15 Viscoelasticity ● S-27

Temperature (°F) FIGURE 7.29

150 200 250 300 350 400 450 Logarithm of the
104
106 relaxation modulus
versus temperature for
103 crystalline isotactic
105
Relaxation modulus, Er(10) (MPa) (curve A), lightly
102 crosslinked atactic
104

Relaxation modulus (psi)

A
(curve B), and
amorphous (curve C )
10
103 polystyrene. (From A.
V. Tobolsky, Properties
1 and Structures of
B 102
Polymers. Copyright 
10–1 1960 by John Wiley &
10
Sons, New York.
C
Reprinted by
10–2
1 permission of John
Tg Wiley & Sons, Inc.)
10–3
50 100 150 200 250
Temperature (°C)

the temperature at which the polymer decomposes; this material will not experience
melting. For increased crosslinking, the magnitude of the plateau Er (10) value will
also increase. Rubber or elastomeric materials display this type of behavior and
are ordinarily utilized at temperatures within this plateau range.
Also shown in Figure 7.29 is the temperature dependence for an almost totally
crystalline isotactic polystyrene (curve A). The decrease in Er (10) at Tg is much
less pronounced than the other polystyrene materials since only a small volume
fraction of this material is amorphous and experiences the glass transition. Further-
more, the relaxation modulus is maintained at a relatively high value with increasing
temperature until its melting temperature Tm is approached. From Figure 7.29, the
melting temperature of this isotactic polystyrene is about 240⬚C (460⬚F).

VISCOELASTIC CREEP
Many polymeric materials are susceptible to time-dependent deformation when the
stress level is maintained constant; such deformation is termed viscoelastic creep.
This type of deformation may be significant even at room temperature and under
modest stresses that lie below the yield strength of the material. For example,
automobile tires may develop flat spots on their contact surfaces when the automo-
bile is parked for prolonged time periods. Creep tests on polymers are conducted
in the same manner as for metals (Chapter 9); that is, a stress (normally tensile)
is applied instantaneously and is maintained at a constant level while strain is
measured as a function of time. Furthermore, the tests are performed under isother-
mal conditions. Creep results are represented as a time-dependent creep modulus
Ec (t), defined by
␴0
Ec (t) ⫽ (7.24)
⑀(t)
wherein ␴0 is the constant applied stress and ⑀(t) is the time-dependent strain. The
creep modulus is also temperature sensitive and diminishes with increasing temper-
ature.
S-28 ● Chapter 7 / Mechanical Properties

With regard to the influence of molecular structure on the creep characteristics,

as a general rule the susceptibility to creep decreases [i.e., Ec (t) increases] as the
degree of crystallinity increases.

7.19 VARIABILITY OF MATERIAL PROPERTIES

COMPUTATION OF AVERAGE AND STANDARD
DEVIATION VALUES
An average value is obtained by dividing the sum of all measured values by the
number of measurements taken. In mathematical terms, the average x of some
parameter x is

冘x
n

i⫽1
i

x⫽ (7.26)
n

where n is the number of observations or measurements and xi is the value of a

discrete measurement.
Furthermore, the standard deviation s is determined using the following ex-
pression:

冘 (x ⫺ x)
1/2

冤 冥
n
2
i
i⫽1
s⫽ (7.27)
n⫺1

where xi , x, and n are defined above. A large value of the standard deviation
corresponds to a high degree of scatter.

EXAMPLE PROBLEM 7.6

The following tensile strengths were measured for four specimens of the same
steel alloy:

Tensile Strength
Sample Number (MPa)
1 520
2 512
3 515
4 522

(a) Compute the average tensile strength.

(b) Determine the standard deviation.
 7.19 Variability of Material Properties ● S-29

S OLUTION
(a) The average tensile strength (TS) is computed using Equation 7.26 with
n ⫽ 4:

冘 (TS )
4

i⫽1
i

TS ⫽
4
520 ⫹ 512 ⫹ 515 ⫹ 522
⫽
4
⫽ 517 MPa
(b) And for the standard deviation, using Equation 7.27,

冘 兵(TS ) ⫺ TS 其
1/2

冤 冥
4
2
i
i⫽1
s⫽
4⫺1

⫽ 冋
(520 ⫺ 517)2 ⫹ (512 ⫺ 517)2 ⫹ (515 ⫺ 517)2 ⫹ (522 ⫺ 517)2
4⫺1
册
1/2

⫽ 4.6 MPa
Figure 7.32 presents the tensile strength by specimen number for this exam-
ple problem, and also how the data may be represented in graphical form. The
tensile strength data point (Figure 7.32b) corresponds to the average value

525 525

TS + s
Tensile strength (MPa)

Tensile strength (MPa)

520 520

TS

515 515

TS ⫺ s

510 510
1 2 3 4
Sample number
(a) (b)

FIGURE 7.32 (a) Tensile strength data associated with Example Problem 7.6. (b)
The manner in which these data could be plotted. The data point corresponds to
the average value of the tensile strength (TS ); error bars that indicate the
degree of scatter correspond to the average value plus and minus the standard
deviation (TS ⫾ s).
S-30 ● Chapter 7 / Mechanical Properties

TS, whereas scatter is depicted by error bars (short horizontal lines) situated
above and below the data point symbol and connected to this symbol by vertical
lines. The upper error bar is positioned at a value of the average value plus
the standard deviation (TS ⫹ s), whereas the lower error bar corresponds to
the average minus the standard deviation (TS ⫺ s).