Mckeen 2015

1 Introduction to Creep, Polymers,
Plastics and Elastomers
1.1 Introduction by a detailed look at creep, including creep-specific

tests and creep graphs. The discussion takes a look
In an earlier book of this series, The Effect at what happens at the microscopic level when
of Temperature and Other Factors on Plastics plastics exhibit creep.
and Elastomers [1], the general mechanical prop-
erties of plastics were discussed. The mechanical
properties as a function of temperature, humidity, 1.2 Types of Stress
and other factors were presented in graphs or
tables. That work includes hundreds of graphs Creep is the time-dependent change in the
of stress versus strain, modulus versus tempera- dimensions of a plastic article when subjected to a
ture, and impact strength versus temperature. constant stress. Stress can be applied in a number
However, when one starts designing products of ways. Normal stress (σ) is the ratio of the
made of plastic, these graphs do not supply all applied force (F) over the cross-sectional area (A)
the necessary information. This is because these as shown in Eq. (1.1).
graphs show the results of relatively short-term
tests. The value in design is in the initial selec- F
σ5 (1.1)
tion of materials in terms of stiffness, strength, A
etc. Designs based on that short-term data
obtained from a short-term test would not predict
accurately the long-term behavior of plastics. 1.2.1 Tensile and Compressive
This is partly because plastics are viscoelastic Stress
materials. Viscoelastic by definition means pos-
sessing properties that are both solid-like and When the applied force is applied directed away
liquid-like. More precisely in reference to plas- from the part, as shown in Figure 1.1, it is a tensile
tics, viscoelastic means that measurements such force inducing a tensile stress. When the force is
as modulus, impact strength, and coefficient of applied toward the part it is a compressive force
friction (COF) are not only sensitive to straining inducing a compressive stress.
rate, temperature, humidity, etc. but also to
elapsed time and loading history. 1.2.2 Shear Stress
The manufacturing method used for the plastic Shear stress (τ) is also expressed as force per
product can also create changes in the structure unit area as in Eq. (1.2).
of the material which have a pronounced effect The shear force is applied parallel to the cross-
on properties. sectional area “A” as shown in Figure 1.2.
The rest of this chapter first deals with the types
of stress and a short introduction to creep. Then the
chemistry of plastics is discussed and because plas- 1.2.3 Torsional Stress
tics are polymeric materials the focus is more on Torsional stress (τ) occurs when a part such as a
polymer chemistry. The discussion includes poly- rod for shaft is twisted as in Figure 1.3. This is also
merization chemistry and the different types of a shear stress, but the stress is variable and depends
polymers and how they can differ from each other. how far the point of interest is from the center of
Since plastics are rarely “neat,” reinforcement, fil- the shaft. The equation describing this is shown
lers, and additives are reviewed. This is followed in Eq. (1.2).
McKeen: The Effect of Creep and other Time Related Factors on Plastics and Elastomers.
DOI: http://dx.doi.org/10.1016/B978-0-323-35313-7.00001-8
© 2015 Elsevier Inc. All rights reserved. 1
2 THE EFFECT OF CREEP AND OTHER TIME RELATED FACTORS ON PLASTICS AND ELASTOMERS
Tc
τ5 (1.2)
K
In this equation, T is the torque and c is the dis-

tance from the center of the shaft or rod. K is a tor-
sional constant that is dependent on the geometry
of the shaft, rod, or beam. The torque (T) is further
defined by Eq. (1.3), in which θ is the angle of
twist, G is the modulus of rigidity (material depen-
dent), and L is the length.
θKG
T5 (1.3)
L
Figure 1.1 Illustration of tensile stress and
compressive stress.
The torsional constant (K) is dependent upon
geometry and the formulas for several geome-
tries are shown in Figure 1.4. Additional
formulas for torsional constant are published [2,
pp. 6376].
1.2.4 Flexural or Bending Stress

Bending stress or flexural stress commonly
occurs in two instances, shown in Figure 1.5.
One is called a simply supported structural beam
bending and the other is called cantilever bending.
Figure 1.2 Illustration of shear stress.
For the simply supported structural beam, the upper
surface of the bending beam is in compression and
the bottom surface is in tension. NA is a region of
zero stress. The bending stress (σ) is defined by
Eq. (1.4). M is the bending moment, which is calcu-
lated by multiplying a force by the distance between
that point of interest and the force. c is the distance
from NA (Figure 1.5) and I is the moment of inertia.
The cantilevered beam configuration is also shown
in Figure 1.5 and has a similar formula. The
formulas for M, c, and I can be complex, depending
on the exact configuration and beam shape, but
Figure 1.3 Illustration of torsional stress. many are published [2, pp. 4653, 547555].
Figure 1.4 Torsional constants for rods or beams of common geometries.

1: INTRODUCTION TO CREEP, POLYMERS, PLASTICS AND ELASTOMERS 3
Figure 1.7 Illustration of hoop stress.
circumferentially. Figure 1.7 shows stresses caused

by pressure (P) inside a cylindrical vessel.
The hoop stress is indicated in the right side of
Figure 1.7 that shows a segment of the pipe.
The classic equation for hoop stress created by
an internal pressure on a thin wall cylindrical pres-
sure vessel is given in Eq. (1.5):
Figure 1.5 Illustration of flexural or bending stress.
Pr
σh 5 (1.5)
t
where:
P 5 the internal pressure

t 5 the wall thickness
r 5 is the radius of the cylinder.
The SI unit for P is Pascal (Pa), while t and r are

in meters (m).
If the pipe is closed on the ends, any force
applied to them by internal pressure will induce an
axial or longitudinal stress (σl) on the same pipe
wall. The longitudinal stress under the same condi-
tions of Figure 1.7 is given by Eq. (1.6)
Figure 1.6 Picture of a three point flexural or
σh
bending test being done in an Instron universal σl 5 (1.6)
testing machine [3]. 2
There could also be a radial stress especially

A picture of a supported beam bending test in an when the pipe walls are thick, but thin-walled sec-
Instron is shown in Figure 1.6. tions often have negligibly small radial stress (σr).
The stress in radial direction at a point in the tube
Mc
σ5 (1.4) or cylinder wall is shown in Eq. (1.7).
I

a2 P b2
σr 5 2 12 2 (1.7)
1.2.5 Hoop Stress b 2 a2 r
Hoop stress (σh) is mechanical stress defined
for rotationally symmetric objects such as pipe or where:
tubing. The real world view of hoop stress is the
tension applied to the iron bands, or hoops, of a P 5 internal pressure in the tube or cylinder
wooden barrel. It is the result of forces acting a 5 internal radius of tube or cylinder
b 5 external radius of tube or cylinder

r 5 radius to point in tube where radial stress is
calculated.
Often the stresses in pipe are combined into a

measure called equivalent stress. This is determined
using the Von Mises equivalent stress formula
which is shown in Eq. (1.8):
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
σe 5 σ2l 1 σ2h 2 σl σh 1 3τ 2c (1.8)
where:
σl 5 longitudinal stress
Figure 1.8 Illustration of flexural creep.
σh 5 hoop stress
τ c 5 tangential shear stress (from material flow-
ing through the pipe).
Failure by fracture in cylindrical vessels is domi-

nated by the hoop stress in the absence of other
external loads because it is the largest principal
stress. Failure by yielding is affected by an equiva-
lent stress that includes hoop stress, and longitudinal
stress. The equivalent stress can also include tangen-
tial shear stress and radial stress when present.
1.3 Basic Concepts of Creep

As noted earlier, creep is the time-dependent Figure 1.9 Illustration of tensile creep.
change in the dimensions of a plastic article when
subjected to a constant stress. Metals also possess Creep is the time-dependent change in the
creep properties, but at room temperature the creep dimensions of a plastic article when subjected to
behavior of metals is usually negligible. Therefore, stress. This is shown schematically in Figure 1.8
metal design procedures are simpler because the for flexural creep. A given load is shown on a plas-
modulus may be regarded as a constant (except at tic plaque supported at the ends. The weight or
high temperatures). However, the modulus of a load along with gravity supplies a constant stress
plastic is not a constant. Provided its variation is on the plastic plaque. After 10 h in this condition
known then the creep behavior of plastics can there is very little deflection or sagging of the plas-
be compensated for using accurate and well- tic plaque. However, after 100 h the deflection, or
established design procedures or by modification of strain, has increased. It is deflected even further
the plastics composition with reinforcing fillers. after 1000 h. The creep measured by the method in
For metals, the objective of the design method is Figure 1.9 is called tensile creep. If the force
usually to determine stress values which will not squeezes on the plastic plaque then the creep mea-
cause fracture. However, for plastics it is more sure would be compressive creep.
likely that excessive deformation will be the limit- If one plots the deflection versus time a plot like
ing factor in the selection of working stresses. This the first part (AB) of that shown in Figure 1.10
book looks specifically at the deformation behavior might be obtained. If the stress (or weight) is
of plastics. removed at point B, the strain or deflection
Figure 1.10 Illustration of elastic recovery, viscous recovery and permanent deflection or creep.
recovers partially very rapidly to point C. That part constant strain rate (steady state) and increasing
is called the elastic recovery. After point C, there is strain rate (tertiary).
a slow viscous recovery to some final point D. The The first stage of creep shown in Figure 1.11 is
plaque is no longer flat and that remaining deflec- named the primary creep region, but it is also
tion is permanent. Creep is the permanent deforma- known as transient creep stage. Primary creep strain
tion resulting from prolonged application of stress is often less than 1% of the sum of the elastic, stea-
below the elastic limit. dy state, and primary strains. The second stage of
Creep and other creep-related properties creep shown in Figure 1.11 is the steady state
(discussed later) are among the most important region or secondary creep. This region is so named
mechanical characteristics of plastics. Plastics that because the strain rate is constant.
have significant time sensitivity at use temperature When the amount of strain is high creep fracture
will have limited value for structural applications or rupture will occur. This is called the tertiary
or applications demanding dimensional stability. region and is also known as accelerating creep stage.
The high strains in this region will start to cause
1.3.1 Categories, Stages, necking or other failure in the material. Necking will
cause an increase in the local stress of the component
or Regions of Creep that further accelerates the strain. The importance of
When one does a tensile creep experiment, such the tertiary region to normal operation and creep
as that shown in Figure 1.9, and the data are design criteria is minimal, as plastic parts are
graphed, a plot like that shown in Figure 1.11 may designed to avoid this region as failure is imminent.
be obtained. Creep data in this plot can be subdi- In Figure 1.11, the timescale of the tertiary region is
vided into three categories (also called stages or greatly expanded for the purpose of clarity.
regions): primary, steady state, and tertiary creep. Considering the small amount of time in addition to
These occur sequentially as shown in Figure 1.11. the fact that the tertiary region develops a plastic
Initially, when the stress is applied, there is an ini- instability similar to necking, operating in the tertiary
tial strain which is an elastic component to the region is not feasible. Therefore, it is a conservative
strain. For that portion, if the stress is removed the estimate to approximate the end of serviceable life of
material returns to its original shape and dimen- any component to coincide with the end of the steady
sions. Considering that the slope of the curve gives state creep region.
the strain rate, the three categories correspond to Whether these regions have any significance other
a decreasing strain rate (primary), approximately than as arbitrary divisions of the curve is an arguable
Figure 1.11 Strain versus time creep behavior.
point. However, this region concept is commonly

discussed in the literature. However, creep data are
rarely found that exhibit a true straight line over a
substantial region of the creep curve. In the past
many of the analyses that have been made of stress
problems for creep have been based on an assump-
tion that the entire creep curve could be represented
by a straight line, that is, a constant rate of creep.
While this may be an adequate way of treating
design problems involving creep at low stresses over
long periods of time, it is hardly adequate for many
present-day problems which often involve high stres-
ses, high temperatures, and short times.
The curve shown in Figure 1.11 was measured
at one amount of stress, determined by the weight
used in Figure 1.9. Families of these curves are
often generated at different amounts of stress and
at different temperatures. Increasing the amount of
stress, logically increases the magnitude of creep
measured. Increasing the temperature has a similar
Figure 1.12 The effect of temperature and stress
effect. The qualitative effect of increasing the stress
on strain versus time creep behavior.
and temperature on the strain versus time creep
curves is shown in Figure 1.12.
1.3.2.1 Stress, Strain, and Time
1.3.2 Measures of Creep The most common method of displaying the
This section covers the various ways to plot interdependence of stress, strain, and time is by
multipoint creep data and the ways the data are means of creep curves. Ideally, the display of the
obtained. interdependence of stress, strain, and time for a
particular plastics material at a specific temperature the 3D plot is represented by a series of two-
is a three-dimensional (3D) plot such as that shown dimensional (2D) plots of these data.
in Figure 1.13. Some of the measured curves that were used to
In practice, it is most common to have the construct the 3D plot are shown in Figure 1.14. The
straintime data (at a given stress) since these can curves at low stress are not shown. The relationship
be obtained by the relatively simple experiments of these curves to the 3D plot is shown by the pla-
described previously in Figures 1.7 and 1.8. By col- nar slices shown in Figure 1.15.
lecting a series of the straintime curves at differ- If the 3D plot is sliced by a series of planes that
ent stress levels the 3D plot can be constructed. 3D correspond to constant time, such as shown in
plots are hard to work visually or practically so Figure 1.16, a plot known as an isochronous creep
plot is obtained. An isochronous plot of the data
used to construct Figure 1.12 is given in
Figure 1.17. Isochronous plots are commonly avail-
able from manufacturers of engineering plastics and
are very familiar to engineers. Besides being useful
plots that data can be obtained by experiment rela-
tively easily because they can also be obtained
experimentally by performing a series of mini-
creep and recovery tests on a plastic. These mini-
creep and recovery tests are less time consuming
and require less specimen preparation than creep
curves. To do this a stress is applied to a plastic
test plaque and the strain is recorded after a time, t
(often at 100 s). The stress is then removed and
the plastic plaque is allowed to recover, generally
for a period of 4t. Next a larger stress is applied
to the same test specimen and after recording the
Figure 1.13 Hypothetical stressstraintime plot strain at time t, this stress is removed and the
for a typical plastic material. material allowed to recover in the same manner.
Figure 1.14 Measured creep plots used to construct Figure 1.13.

Figure 1.15 A plane at constant stress slices the Figure 1.16 A plane at constant time slices the
stressstraintime plot. stressstraintime plot.
Figure 1.17 Isochronous creep plot obtained from Figure 1.13.
This procedure is repeated until enough points have Isometric and isochronous plots are the most
been obtained for the isochronous graph to be plot- common graphical representation of creep data.
ted. Additional times may be run, but they are typi- They can be measured in flexure, tension, or com-
cally increased by an order of magnitude, so usually pression. They are also measured at a specific tem-
only one or two curves are measured by this method. perature, so it is common to have families of these
When the plane is at constant strain as shown in curves at different temperatures.
Figure 1.18, the plots shown in Figure 1.19 are
obtained. These are called isometric curves. Isometric
curves are an indication of the relaxation of stress in
1.3.2.2 Creep Modulus
the material when the strain is kept constant. Isometric Elastic modulus is equal to stress divided by
data are often used as a good approximation of stress strain as shown in Eq. (1.9). However, when creep
relaxation in a plastic since stress relaxation is a less has occurred there is an amount of strain that gets
common experimental procedure than creep testing. added into the denominator of the equation, the
Figure 1.18 A plane at constant strain slices the stressstraintime plot.
Figure 1.19 Isometric plot obtained from Figure 1.13.
modulus so calculated is called the apparent creep are obtained from an isometric (constant strain,
modulus as shown in Eq. (1.10). Figure 1.19) curve then this is a relaxation modulus.
The creep modulus curve may be obtained from con-
Elastic modulus 5 stress=strain ðwith no creepÞ (1.9) stant stress curves (Figure 1.14) by dividing the con-
stant creep stress by the strain at various times.
Apparent creep modulus 5 stress=ðstrain 1 creepÞ Both the creep and relaxation modulus will
decrease as time increases, as shown in
(1.10)
Figure 1.20. The plot is usually shown using
loglog scales. Creep modulus is sometime called
A plot of apparent creep modulus (often shortened apparent modulus or apparent creep modulus. The
to just creep modulus) versus time is a common way reason “apparent” is used is to be more explicit
to show creep performance. A generic creep modulus about how the calculation of creep or relaxation
versus time plot is shown in Figure 1.20. If the data modulus is done.
Figure 1.20 Typical variation of creep or relaxation modulus with a wide range of time.
Figure 1.21 Apparent modulus versus time at various temperatures for a typical plastic material.
Figure 1.21 shows the apparent modulus versus 1.3.2.3 Creep Strength and Rupture
time for a plastic material at various temperatures at a Strength
given stress level. This figure does not cover as wide Creep strength and rupture strength are com-
a range in time as Figure 1.20. As the temperature monly used when designing or using pipe or tubing.
goes up, one would expect the creep part of the Rupture strength is defined as the stress at specified
deflections to be larger (and the modulus to be lower) environmental conditions (temperature, humidity and
and this is shown in the figure. This plot is one of sev- sometimes chemical environment) to produce rupture
eral common ways to plot the effects of creep. in a fixed amount of time usually given in hours.
Figure 1.22 Graphical explanation of creep rupture, stress rupture, and creep rupture envelope.
creep strain is the sum of the permanent creep

strain (Figure 1.10, also called permanent deflec-
tion) plus the recoverable creep strain. The creep
failure deformation can be defined by the design
engineer as the point at which the part ceases to
function as intended. Stress rupture often is defined
as onset of the third stage of creep (Figure 1.20).
Creep rupture extends the creep process through
stage 3 to the limiting condition where the stressed
part actually breaks into two parts. Many engineers
often use stress rupture interchangeably with creep
rupture. Figure 1.22 illustrates these differences.
Figure 1.23 shows a plot of creep rupture envel-
opes at several temperatures. These plots are very
common for materials that are use in pipes. Creep
rupture analysis generates a time to failure data for
different constant stress levels. These data can be
used to predict the life of a component and can be
used in design calculations.
Over a long period of time at constant load,
most polymers will creep, leading eventually to
failure. Aggressive environments, such as humid,
oxidizing, or acidic atmospheres, generally acceler-
ate failure as shown in Figure 1.24.
Figure 1.23 Creep rupture stress (envelopes) It is important to keep in mind that creep mea-
versus time of a typical polycarbonate at various sures on pipes generate a time to failure curve
temperatures. under static stress conditions. Pipe usually has
material flowing through it that can also have an
Creep failure occurs when the accumulated effect on creep. This was mentioned in the discus-
creep strain results in a deformation of the machine sion of hoop stress and equivalent stress in
part that exceeds the design limits. Accumulated Section 1.2.5.
Figure 1.24 Typical creep rupture curves in air and environment.
of plastic pipes. The superposition technique starts

out by measuring creep rupture curves at several
temperatures above the temperature for the long-
term plot. Timetemperature superposition implies
that the response time function of the elastic modu-
lus at a certain temperature resembles the shape of
the same functions of adjacent temperatures. An
example of this stress/time to failure data is shown
in Figure 1.25.
Then starting the highest temperature curve, T5
in the figure, is shifted to the right until most of it
fits over the next highest temperature, T4. Then the
combined T5 1 T4 curve is shifted to fit over the
T3 curve. This is all done “by eye” and the process
is shown in Figure 1.26.
The final master curve, shown in Figure 1.27,
can then be used to establish the failure stress of
the plastic pipe material in the environment at the
Figure 1.25 Typical creep rupture curves for a service temperature and at the desired life of the
plastic pipe at various temperatures. component.
Creep strength is defined as the stress at specified
Many time to fail type plots run out to 50 years environmental conditions that produces a steady
or more. Creep experiments have not been run for creep rate, such as 1%, 2%, or 5%. A plot of creep
that length of time. Long-term creep is generally strength of polyethylene pipe at 20°C is shown in
predicted by tests that are carried out at elevated Figure 1.28. In this case, the creep strength is shown
temperature. Then, the long-term data are predicted in areas due to uncertainty coming for limited exper-
using timetemperature superposition techniques. imental data. Creep strength values are determined
Timetemperature superposition is well established from isometric plots such as shown in Figure 1.14.
(ISO 1167 Standard) and is used extensively in the An alternate term is creep limit. As a rule, creep
assessment of the long-term (50 year) design stress strength is expressed as the creep rupture strength
Figure 1.26 Creep rupture curve shifts at various temperatures used to produce a long-term master curve.
Figure 1.27 Typical creep rupture master curve used to assess the long-term failure stress of a material.
(i.e., the stress that causes rupture after 10,000 or curve of creep modulus versus shifted time cover-
100,000 h). ing the full range of available data. Therefore, a
shifted time span of 109 hours is covered.
The amount of time that each temperature line gets
1.3.2.4 Temperature Shift Factors shifted in generating the line in Figure 1.30 is noted
Often the modulus is found to be reasonably inde- and a separate graph is plotted versus that tempera-
pendent of stress level [4]. Plots of modulus versus ture. This produces the temperature shift factor plot
time at various temperatures will produce a series of such as that shown in Figure 1.31.
parallel straight lines as shown in Figure 1.29. The temperature shift factor plot in Figure 1.31
The data for temperatures above 23°C in can be used to estimate the flexural creep modu-
Figure 1.29 can be shifted to the right to create a lus at any temperature within the range of the
single line that extends the time to many more original data. The temperature shift factor at the
hours. This is shown in Figure 1.30, the master desired temperature is read as indicated with
Figure 1.28 Creep strength and creep rupture comparison for polyethylene pipe measured at 20°C.
Figure 1.29 Flexural creep modulus in three point bending for acetal copolymer at five different temperatures [4].
the dotted lines in the figure. The temperature of 20,000 h is multiplied by 1600 to give a shifted
shift factor is essentially a time multiplier that time of 3.2 3 107 hours. At 3.2 3 107 hours, a
shifts the time axis for the reference creep modu- flexural modulus of 590 MPa is read from
lus curve in Figure 1.30 to the predicted time axis Figure 1.30.
at the desired temperature. The actual time of
interest is multiplied by the temperature shift fac-
1.3.2.5 Compression Set
tor to give shifted time that is used in Figure 1.30
to determine the appropriate modulus. For exam- Compression set is often a property of interest
ple, to estimate the flexural creep modulus at when using elastomers. Compression set is the
60°C and 20,000 h, the temperature shift factor is amount of permanent deformation that occurs when
about 1600 (from Figure 1.31). The desired time a material is compressed to a specific deformation,
Figure 1.30 Flexural creep modulus in three point bending for acetal copolymer at 23°C by timetemperature
shifting [4].
Figure 1.31 A temperature shift factor plot for acetal copolymer [4].
for a specified time, at a specific temperature. elastomer regained only 60% of its uncompressed
ASTM D395 Standard Test Methods for Rubber thickness. A compression set of 100% says that the
Property—Compression Set is the test method used thermoplastic elastomer never recovers—it remains
and it calls for the material to be 25% deformed compressed. Often creep is confused with compres-
(compressed) for a given period. After a 30-min sion set. However, compression set is the amount
recovery time, the sample is measured. The value of deformation under a constant strain, whereas
derived is the percentage a material sample fails to creep is the amount of deformation under a con-
recover of its original height. For example, a com- stant stress. Data on compression set were included
pression set of 40% states that the thermoplastic in this work for this reason.
1.3.2.6 Environmental Stress Cracking These occur without irreversible chemical

changes in the polymer(s) in the plastic material.
Environmental stress cracking (ESC) is a com-
ESC is differentiated from stress corrosion cracking
mon cause of plastic product failure. ESC may be
(SCC), which by definition must involve stress and
defined as the acceleration of stress cracking by
polymer degradation.
contact with a liquid or vapor without chemical
It is important to note that the fluid only acceler-
degradation of the plastic. An illustration of the
ates the mechanism as stress cracking will eventu-
simplest test helps define ESC better.
ally occur in the absence of an active fluid. It will
There are many tests for ESC [5, pp. 1319]
eventually occur in air.
and they are summarized in the following sections.
The maximum applied stress (σ) is given by the
Single Cantilever Test following equation:
This simple test is a single cantilever beam test and
is illustrated in Figure 1.32. This test requires essen- 6FL
σ5 (1.11)
tially no investment. As shown in Figure 1.32 a strip wt2
of the plastic material is clamped to the edge of a
sturdy bench. The test fluid is applied to the upper where:
surface of the test plaque. Viscous nonvolatile fluids
such as oils and greases can be smeared onto the sur- F 5 the applied load in Newtons
face. Volatile test fluids need to be applied continu- w 5 beam width in mm
ously. A weight is applied to the end to provide a L 5 effective beam length in mm
constant stress. A control is recommended to be run
t 5 beam thickness in mm.
concurrently in the absence of the fluid. The area
under the test fluid is examined periodically for the
The maximum applied stress ordinarily should
formation of cracks or other defects. Details on this
be as high as possible. It should exceed the
test will be provided later in the ESC testing section.
expected service stress. If this is not known a rea-
The mechanism of stress cracking is purely
sonable starting point of 20 N/mm2 should be
physical. The interactions between the fluid, the
applied. A dry control should always be run at the
stress, and the plastic polymer include:
same time. If the vapor pressure of the contact fluid
is high enough that evaporation occurs, then the
1. Local yielding
fluid must be periodically or continuously replen-
2. Fluid absorption ished. The surface in contact with the fluid and the
3. Plasticization control surface should be compared periodically
4. Craze initiation using a magnifying glass.
5. Crack growth Three Point Bending Test
6. Fracture. The three point bending test imparts a deflection
to the middle of a test plaque or beam. Two com-
mon devices are shown in Figures 1.33 and 1.34.
Figure 1.33 shows a device that can impart a vari-
able deflection by means of a screw adjustment.
The device in Figure 1.34 is deflected by a pin.
The pin can be machined to different diameters
allowing for different strain levels. The test device
can be placed in the test fluid.
The maximum surface strain (εmax) can be calcu-
lated using the equation:

6δt
εmax 5 3 100% (1.12)
Figure 1.32 Single cantilever beam, ESC test L
under constant stress.
Figure 1.33 Three point bending ESC test device

with variable imparted strain. Figure 1.34 Three point bending ESC test device.
Figure 1.35 Three point bending ESC test of a plastic in contact with tri-n-butyl phosphate.
where: tensile stress and the recording of time to rup-

ture. In this test, the change in length (strain
δ 5 the midpoint deflection in mm response) of a material subjected to a constant
L 5 effective beam length in mm tensile stress is monitored. The test employs a
Rapra tensile creep machine, a diagram of which
t 5 material thickness in mm. is shown in Figure 1.36. The change in length is
measured using a Moiré fringe extensometer (not
Strains are typically less than or equal to 1%. shown).
The results are usually plotted as applied strain ver- The test is usually run in air or the fluid or gas
sus time until visible cracking as shown in of interest. Typical data obtained by this test are
Figure 1.35. shown in Figure 1.37. The break of the strain ver-
Tensile Creep Rupture Test sus time curves at a given stress level is assumed
The tensile creep rupture test is preferred and to be the initiation of ESC. For transparent plastics
the most direct method of quantifying ESC this point coincides with the appearance of visible
performance. It involves the application of a crazing.
Figure 1.36 Rapra tensile creep machine.
Figure 1.37 Typical tensile creep curves of a polymer in air and in contact with an ESC fluid.
ESC Performance Expectations more prone to ESC than either semicrystal-

Based on the evidence of published data and the line thermoplastics or thermosets.
incidence of ESC, the following generalizations
about ESC performance may be made [5, pp. 910]: 2. Fluids with modest hydrogen bonding are most
likely to be severe or moderate ESC agents.
1. Amorphous thermoplastics or thermoplastics These include organic fluids classed as aro-
in their amorphous state are considerably matic hydrocarbons, halogenated hydrocarbons,
Table 1.1 Standard Tests
Measurement ASTM ISO

Flexural creep ASTM D2990 ISO 899-2
Tensile creep ASTM D2990 ISO 899-1
Compressive creep ASTM D2990
Creep rupture ASTM D2990
Flexural creep modulus ISO 6602
a
Stress relaxation in compression ASTM D2991 ISO 3384
Stress relaxation in tension ISO 6914
Thermoplastic pipes resistance to internal pressure ISO 1167
Poisson’s ratio ASTM E132
Standard guide for material properties ASTM D5592
needed in engineering design
Environmental stress cracking ISO 22088
a
Withdrawn but often still referenced.
ethers, ketones, aldehydes, esters, and nitrogen 1.3.2.7 Summary of Creep

and sulfur-containing compounds. Non- Standard Tests
hydrogen-bonded fluids such as aliphatic
Standard plastics tests are generally specified
hydrocarbons and highly hydrogen-bonded
primarily by two standards organizations. ASTM
fluids such as water and alcohols tend to be
International, originally known as the American
milder ESC agents.
Society for Testing and Materials (ASTM) is one
3. Fluids with a high molar volume are less likely organization; its standards are the well-known
to be severe stress cracking agents. Such fluids ASTM standards. The second organization is the
tend to have high viscosity and high boiling International Organization for Standardization,
points. Thus low viscosity silicone oil is more abbreviated as ISO, that is also well known. These
aggressive than silicone grease. organizations do not specify just plastics tests, but
4. Fluids are most aggressive at temperatures they both develop technical standards in whatever
near to their boiling point. Thus nitrogen is a fields need them. They are both well accepted, but
stress cracking agent for many plastics at its unfortunately they do not always agree exactly.
boiling point (2196°C). While there is often one-to-one correlation of
ASTM and ISO standards, they may differ in proce-
5. Amorphous plastics are most susceptible to dure and conditions, which may lead to slightly dif-
ESC at temperatures that approach their glass ferent measures. These standard tests are listed
transition temperature, Tg. (A simplified defi- in Table 1.1.
nition of the glass transition temperature is ASTM D2990-01 Standard Test Methods for
the temperature at which an amorphous Tensile, Compressive, and Flexural Creep and
plastic becomes brittle on cooling, or soft on Creep Rupture of Plastics describes the measure-
heating.) As the Tg of most amorphous plas- ment of creep and creep rupture properties of plas-
tics is well above their recommended maxi- tics under specified environmental conditions,
mum service temperature this means that in primarily temperature and humidity. The method is
practice the resistance of a plastic to ESC a good reference as it describes test apparatus, cal-
reduces with increasing service temperature. culations, and includes background discussion on
6. Low-molecular-weight grades have reduced basic concepts. It is similar to the three parts of
ESC resistance. ISO 899.
ISO 899-1:2003 Plastics—Determination of ISO 1167 is focused on testing of pipe under inter-
creep behavior—Part 1: Tensile creep specifies a nal pressure. ISO 1167-1:2006 Thermoplastics pipes,
method for determining the tensile creep of plastics fittings and assemblies for the conveyance of fluids—
in the form of standard test specimens under speci- Determination of the resistance to internal pressure—
fied conditions such as those of pretreatment, tem- Part 1: General method specifies a general test
perature, and humidity. The method is suitable for method for determining the resistance to internal
use with rigid and semirigid nonreinforced, filled hydrostatic pressure at a given temperature of thermo-
and fiber-reinforced plastics. The test sample is plastics pipes, fittings, and piping systems for the
dumb-bell-shaped and is molded directly or transport of fluids. The method accommodates water-
machined from sheets or molded articles. in-water, water-in-air, and water-in-liquid tests.
ISO 899-2:2003 Plastics—Determination of ISO 1167-2:2006 Thermoplastics pipes, fittings
creep behavior—Part 2: Flexural creep by three and assemblies for the conveyance of fluids—
point loading specifies a method for determining Determination of the resistance to internal pressure—
the flexural creep of plastics in the form of standard Part 2: Preparation of pipe test pieces specifies the
test specimens under specified conditions such as dimensions and method for preparation of extruded
those of pretreatment, temperature, and humidity. or injection-molded tubular test pieces. ISO 1167-
It uses the simple freely supported beam loaded 3:2007 Thermoplastics pipes, fittings and assemblies
at mid-span configuration shown in Figure 1.8. for the conveyance of fluids—Determination of the
The method is suitable for use with rigid and resistance to internal pressure—Part 3: Preparation
semirigid nonreinforced, filled, and fiber-reinforced of components specifies the procedure for the
plastics. The test sample is dumb-bell-shaped and preparation of components. ISO 1167-4:2007
is molded directly or machined from sheets or Thermoplastics pipes, fittings and assemblies for the
molded articles. conveyance of fluids—Determination of the resistance
ISO 3384:2005 Rubber, vulcanized or to internal pressure—Part 4: Preparation of assem-
thermoplastic—Determination of stress relaxation in blies specifies the procedure for the preparation of
compression at ambient and at elevated tempera- test assemblies.
tures. It specifies two methods for determining stress ISO 22088-1:2006 Plastics—Determination of
relaxation in compression, using cylindrical or rings resistance to ESC—Part 1: General guidance. ISO
test pieces. It also described the determination of 22088-2:2006 Plastics—Determination of resis-
stress relaxation in liquid environments. ASTM test tance to ESC—Part 2: Constant tensile load
D2991-84 Recommended Practice for Testing Stress method. ISO 22088-3:2006 Plastics—
Relaxation of Plastics was similar but has been with- Determination of resistance to ESC—Part 3: Bent
drawn and is not maintained by ASTM any longer, strip method. ISO 22088-4:2006 Plastics—
though it is still occasionally referenced. Determination of resistance to ESC—Part 4: Ball
ISO 6914:2004 Rubber, vulcanized or or pin impression method. ISO 22088-5:2006
thermoplastic—Determination of aging characteristics Plastics—Determination of resistance to ESC—Part
by measurement of stress relaxation describes three 5: Constant tensile deformation method. ISO
methods for measuring stress relaxation in tension of 22088-6:2006 Plastics—Determination of resis-
the rubber vulcanizate. One method is for measure- tance to ESC—Part 6: Slow strain rate method.
ment under continuous strain conditions and two for ASTM D1693-08 Standard Test Method for ESC
measurement under intermittent strain conditions. of Ethylene Plastics.
ASTM D5592-94(2002)e1 Standard Guide for ASTM D 2561 Standard Test Method for
Material Properties Needed in Engineering Design Environmental Stress-Crack Resistance of Blow-
Using PLASTICs is a guide that covers the essential Molded Polyethylene Containers.
material properties needed for designing with plas-
tics. It is intended only as a convenient resource for
engineering design. ISO and ASTM standard meth- 1.4 Plastics and Polymers
ods for the relevant material properties are listed in
this guide for the benefit of design engineers. It A basic understanding of plastic and polymer
also notes that for some of the desired properties, chemistry will make the discussion of creep
no ASTM or ISO standards exist. mechanisms in the next section easier to understand
and it also provides a basis for the introduction of bonds in the monomer. The polymerization process
the plastic families in later chapters. takes place in three distinct steps:
The most basic component of plastic and elasto-
mer materials is polymers. The word polymer is 1. Chain initiation—usually by means of an ini-
derived from the Greek term for “many parts.” tiator which starts the polymerization process.
Polymers are large molecules comprised of many The reactive initiation molecule can be a
repeat units, called monomers that have been chem- radical (free radical polymerization), cation
ically bonded into long chains. Since World War II, (cationic polymerization), anion (anionic
the chemical industry has developed a large quan- polymerization), or/and organometallic com-
tity of synthetic polymers to satisfy the materials plex (coordination polymerization).
needs for a diverse range of products, including 2. Chain propagation—a monomer adds onto
paints, coatings, fibers, films, elastomers, and struc- chain and each new monomer unit creates an
tural plastics. Literally thousands of materials can active site for the next attachment. The net
be called “plastics,” although the term today is typi- result is shown in Figure 1.38.
cally reserved for polymeric materials, excluding
fibers, which can be molded or formed into solid or 3. Chain termination—the radical, cation, or
semisolid objects. As of the beginning of 2014, anion is “neutralized”, stopping the chain
IDES The Plastics Web® (http://www.ides.com) propagation.
listed over 85,900 different grades of plastic from
over 900 suppliers. Many of the plastics discussed in later chapters of
this book are formed in this manner. Some of the
plastics made by addition polymerization include
1.4.1 Polymerization polyethylene, polyvinyl chloride (PVC), acrylics,
Polymerization is the process of chemically polystyrene, and polyoxymethylene (acetal).
bonding monomer building blocks to form large
molecules. Commercial polymer molecules are usu- 1.4.1.2 Condensation Polymerization
ally thousands of repeat units long. Polymerization
can proceed by one of several methods. The two The other common method is condensation poly-
most common methods are called addition and con- merization (also called step-growth polymerization)
densation polymerization. in which the reaction between monomer units
and the growing polymer chain end group releases
a small molecule, often water as shown in
1.4.1.1 Addition Polymerization Figure 1.39. The monomers in this case have two
In addition polymerization (sometimes called reactive groups. This reversible reaction will reach
chain-growth polymerization), a chain reaction equilibrium and halt unless this small molecular
adds new monomer units to the growing polymer by-product is removed. Polyesters and polyamides
molecule one at a time through double or triple are among the plastics made by this process.
Figure 1.38 Addition polymerization.
Figure 1.39 Condensation polymerization.

Understanding the polymerization process used to type are grouped together. A block copolymer can
make a particular plastic gives insight into the nature be thought of as two homopolymers joined together
of the plastic. For example, plastics made via conden- at the ends:
sation polymerization, in which water is released, can
degrade when exposed to water at high temperature.
Polyesters such as polyethylene terephthalate (PET) Block copolymer
can degrade by a process called hydrolysis when
exposed to acidic, basic, or even some neutral envir- A polymer that consists of large grouped blocks
onments severing the polymer chains. The polymer’s of each of the monomers is also considered a block
properties are degraded as a result. copolymer:
1.4.2 Copolymers Block copolymer

A copolymer is a polymer formed when two
(or more) different types of monomers are linked in When chains of a polymer made of monomer B
the same polymer chain, as opposed to a homopoly- are grafted onto a polymer chain of monomer A we
mer where only one monomer is used. If exactly have a graft copolymer:
three monomers are used, it is called a terpolymer.
Monomers are only occasionally symmetric; the
B B
molecular arrangement is the same no matter which
end of the monomer molecule you are looking at. B B
The arrangement of the monomers in a copolymer
B B
can be head-to-tail, head-to-head, or tail-to-tail.
Since a copolymer consists of at least two types of A A A A A A A A A A A A A A A A A
repeating units, copolymers can be classified based B
on how these units are arranged along the chain.
These classifications include: B
B
• Alternating copolymer
B
• Random copolymer (statistical copolymer)
• Block copolymer Branched/grafted copolymer
• Graft copolymer. High-impact polystyrene, or HIPS, is a graft

copolymer. It’s a polystyrene backbone with chains
In the following examples, A and B are different of polybutadiene grafted onto the backbone. The
monomers that do not have to be present in a one- polystyrene gives the material strength, but the rub-
to-one ratio. When the two monomers are arranged bery polybutadiene chains give it resilience to
in an alternating fashion, the polymer is called an make it less brittle.
alternating copolymer:
1.4.3 Linear, Branched, and
Alternating copolymer
Cross-Linked Polymers
Some polymers are linear—a long chain of con-
In a random copolymer, the two monomers may nected monomers. Polyethylene, PVC, Nylon 66,
link in any order: and polymethyl methacrylate are some linear com-
mercial examples found in this book. Branched poly-
mers can be visualized as a linear polymer with side
Random copolymer chains of the same polymer attached to the main
chain. While the branches may in turn be branched,
In a block copolymer, all monomers of one type they do not connect to another polymer chain. The
are grouped together and all monomers of the other ends of the branches are not connected to anything.
Figure 1.40 Linear, branched and cross-linked polymers.
Table 1.2 Dipole Moments in Some Small Molecules
Dipole Dipole Dipole

Molecule Moment Molecule Moment Molecule Moment
H2 0 HF 1.75 CH4 0.0
O2 0 H 2O 1.84 CH3Cl 1.86
N2 0 NH3 1.46 CCl4 0
Cl2 0 NF3 0.24 CO2 0
Br2 0 BF3 0
Special types of branched polymers include star The polarity of a molecule affects the attraction
polymers, comb polymers, brush polymers, dendro- between molecular chains, which affects the struc-
nized polymers [6], ladders, and dendrimers. A ture of the polymer and the attraction of polar
cross-linked polymer, sometimes called network molecules, so one would expect polarity to affect
polymer, is one in which different chains are con- solubility which affects permeability.
nected. Essentially, the branches are connected to How does one predict molecular polarity? When
different polymer chains on the ends. These three there are no polar bonds in a molecule, there is no
polymer structures are shown in Figure 1.40. permanent charge difference between one part of the
molecule and another so the molecule is nonpolar.
1.4.4 Polarity For example, the Cl2 molecule has no polar bonds
because the electron charge is identical on both
A molecule is two or more atoms joined by a atoms. It is therefore a nonpolar molecule. The CaC
covalent bond. Basically the positively charged and CaH bonds in hydrocarbon molecules, such as
atom nuclei share the negatively charged electrons. ethane, C2H6, are not significantly polar, so hydrocar-
However, if the atoms are different they may not bons are nonpolar molecular substances and hydro-
share the electrons equally. The electrons will be carbon polymers like polyethylene or polypropylene
denser around one of the atoms. This would make are nonpolar also.
that end more negatively charged than the other A molecule can possess polar bonds and still be
end and that creates a negative pole and a positive nonpolar, however. If the polar bonds are evenly (or
pole (a dipole), and such a bond is said to be a symmetrically) distributed, the bond dipoles cancel
polar bond and the molecule is polar and has a and do not create a molecular dipole. For example, the
dipole moment. A measure of how much an atom three bonds in a molecule of CCl4 are significantly
attracts electrons is electronegativity. The electro- polar, but they are symmetrically arranged around the
negativity of common atoms in the polymers central carbon atom. No side of the molecule has more
follows: negative or positive charge than another side, and so
the molecule is nonpolar. Dipole moments in some
F . O . Cl and N . Br . C and H small molecules are given in Table 1.2.
High polarity Nylon 6/6

Nylon 6
Polyethylene terephthalate (PET)
Cellulose acetate
Nitrile rubber (NBR) (50% acrylonitrile)
Polyurethane
Nitrocellulose
Epoxy
Polycarbonate (PC) Figure 1.42 Example polymer structures.
Polymethyl methacrylate (PMMA)
Polyvinyl acetate where
Nitrile rubber (NBR) (30% acrylonitrile)
Acrylate elastomers
Polyvinyl butyral • C 5 number of carbons
Polyepichlorohydrin
Cellulose acetate butyrate • N 5 number of nitrogens
Polystyrene • X 5 number of halogens (F, Cl, Br, I)
Polyvinyl alcohol
Polychloroprene • H 5 number of hydrogens
Polyethylene
Nitrile rubber (NBR) (20% acrylonitrile) • Oxygen and sulfur are not included in the for-
Chlorinated polyethylene mula because saturation is unaffected by these
Styrene-butadiene rubber (SBR)
Polybutadiene
elements.
Natural rubber
Halogenated butyl Examples:
Polypropylene
Ethylene propylene diene monomer rubber (EPDM)
Butyl rubber
Ethylene:
2C 1 2 1 N 2 X 2 H
Perfluorinated polymers C2 H4 DoU 5
Low polarity Silicone 2 (1.14)
Figure 1.41 Qualitative ranking of polymer 23212102024
5 51
polarities. 2
Benzene:
Generally, polar polymers are more permeable to 2C 1 2 1 N 2 X 2 H
C6 H6 DoU 5
water than nonpolar polymers. Figure 1.41 shows a 2 (1.15)
qualitative ranking of some polymer polarities. 23612102026
5 54
2
1.4.5 Unsaturation When polymers are used the formula shown is
Up to this point in the discussion of polymer often the repeating unit as shown in Figure 1.42.
chemistry, the atom to atom structure has not This will often have two bonds that are shown to
been discussed. The covalent bonds between which the repeating unit is supposed to attach. If
atoms in a polymer can be single, double, triple applying a DoU formula to the repeating unit one
bonds, or even rings. The presence of bonds high- would remove the “12” in the formula.
er than single bonds generally makes the polymer Examples:
molecule stiffer and reduces freedom of rotation Polyethylene ðPEÞ:
along the polymer chain, and that can affect its 2C 1 N 2 X 2 H
properties. It is easier to discuss molecules first 3ðCH2 3CH2 Þn 2 DoU 5
2
and then extend that discussion to polymers.
232102024
Saturated molecules only contain single bonds 5 50
with no rings. 2
Often when talking about molecular unsatura- (1.16)
tion, the degree of unsaturation (DoU) is noted.
Calculation of the DoU, if the molecular formula is Polyphenylene sulfone ðPPSÞ:
2C 1N 2X 2H
given, uses the formula in Eq. (1.13): 3ðC6 H4 3SÞn 2DoU5
2 (1.17)
2C 1 2 1 N 2 X 2 H 236102024
DoU 5 (1.13) 5 54
2 2
1.4.6 Steric Hindrance

As described earlier in this chapter polymers
are long chains of atoms linked together. They
may be flexible and bendable. To explain this
one may visualize them as a ball and stick model.
In chemistry, the ball and stick model is a molec-
ular model of a chemical substance which aims to
display both the 3D position of the atoms and the
bonds between them. The atoms are typically
represented by spheres, connected by rods which
represent the bonds. Double and triple bonds are
usually represented by two or three curved rods,
respectively. The chemical element of each atom
is often indicated by the sphere’s color and size. Figure 1.43 Steric hinderance shown with a ball
The top of Figure 1.43 shows a drawing of a ball and stick molecular model.
and stick model of a molecule. Figure 1.43 also
indicates that there is free rotation around the sin-
gle bonds. If there was a double or triple bond
there would not be any rotation possible around
those bonds. Similarly, ring structures, while they
might flex a little bit, inhibit rotation. In some
cases, such as shown in the bottom of
Figure 1.44 Structural isomers.
Figure 1.43, large atoms or bulky side groups
might bump into each other as the molecule
rotates around single bonds. This is called steri-
cally hindered or steric hindrance. Hindered or
inhibited rotation stiffens the polymer molecule
and dramatically affects its physical properties.
1.4.7 Isomers
Isomers (from Greek isomerès; isos 5 “equal,”
méros 5 “part”) are compounds with the same
molecular formula but a different arrangement of Figure 1.45 Head to tail isomers [3].
the atoms in space. There are many kinds of iso-
mers and the properties can differ widely or almost different ways to connect neighboring repeating
not at all. units are, headtail, headhead and tailtail.
1.4.7.1 Structural Isomers 1.4.7.2 Geometric Isomers

Structural isomers have the atoms arranged in a When there is a carboncarbon double bond is a
completely different order as shown in Figure 1.44. molecule there might also be two ways to arrange
Here both polymer repeating groups have the same the groups attached to the double bonds. This is
formula, aC4H8a, but the atoms are arranged dif- best seen in side-by-side structures such as shown
ferently. The properties of structural isomers may in Figure 1.46.
be very different from each other. These are called geometric isomers that owe
Often the repeating group in a polymer is exactly their existence to hindered rotation about double
the same formula, but the repeating group is flipped bonds. If the substituents are on the same side of
over as shown in Figure 1.45. If one views the the double bond, then the isomer is referred to as:
repeating group as having a head and a tail then the cis- (Latin: on this side). If the substituents are on
Figure 1.47 The structure of polypropene.
Figure 1.46 cis- and trans-isomers.
Figure 1.48 The structure of atactic polypropene.
Figure 1.49 The structure of isotactic polypropene.
Figure 1.50 3D ball and stick structure of isotactic polypropene [3].
the opposite side of the double bond are referred to some bonds (the dotted lines) are behind the plane
as: trans- (Latin: across). of the paper and others stick out of the paper (the
ones on the ends of the little triangular wedges). In
this structure, some of the methyl (aCH3) groups
1.4.7.3 Stereoisomers: Syndiotactic,
are above the paper plane and others are behind the
Isotactic, Atactic paper plane. This is called atactic polypropene
Stereoisomerism occurs when two or more Atactic polypropene has at random about 50% of
molecules have an identical molecular formula and hydrogen/methyl groups in front/back of CaCaC
the same structural formula (i.e., the atoms are chain viewing plane. This form of polypropene is
arranged in the same order). However, they differ amorphous (noncrystalline) and has an irregular
in the 2D or 3D spatial arrangements of their structure due to the random arrangement of the
bonds—which mean different spatial arrangement methyl groups attached to the main carboncarbon
of the atoms—even though they are bonded in chain. It tends to be softer and more flexible than
the same order. This may best be understood the other forms (described below) and is used for
by example. roofing materials, sealants, and other weatherproof
Polypropylenes all have the same simplified coatings.
structural polymer formula of polypropene as Isotactic polypropene has all of the methyl groups
shown in Figure 1.47. in front of the CaCaC chain viewing plane and all
However, there are subtle differences in the of the Hs at the back as shown in Figure 1.49.
ways to draw this structure. Figure 1.48 shows a Figure 1.50 shows a 3D ball and stick representation
longer structure of polypropene, one that also of isotactic polypropylene. This stereoregular struc-
shows some 3D structure. This structure shows how ture maximizes the moleculemolecule contact and
Figure 1.51 The structure of syndiotactic polypropene.
Figure 1.52 3D ball and stick representation of syndiotactic polypropene [3].
so increases the intermolecular forces compared to carbonyl group, the CQO, likewise is a dipole,
the atactic form. This regular structure is much stron- where the oxygen has the slight negative charge
ger (than the atactic form above) and is used in sheet and the carbon is slightly positive. When polymer
and film form for packaging and carpet fibers. chains line up these hydrogen bonds are formed
Syndiotactic polypropene has a regular alterna- (indicated by the wide gray bar in the left side of
tion of 50% of hydrogen/methyl groups in front/ Figure 1.53), bonds that are far weaker than the
back of aCaCaCachain viewing plane as shown covalent bonds but bonds of significant strength
in Figure 1.51. Figure 1.52 shows a 3D ball and none-the-less.
stick representation of syndiotactic polypropylene. Other side groups on the chain polymer can lend
Its properties are similar to isotactic polypropene the polymer to hydrogen bonding between its own
rather than the atactic form, i.e., the regular poly- chains. These stronger forces typically result in
mer structure produces stronger intermolecular higher tensile strength and higher crystalline melt-
forces and a more crystalline form than the atactic ing points. Polyesters have dipoledipole bonding
polypropene. between the oxygen atoms in CQO groups and the
hydrogen atoms in HaC groups. Dipole bonding is
not as strong as hydrogen bonding.
1.4.8 Inter and Intra Molecular
Attractions in Polymers
1.4.8.2 Van der Waals Forces
The attractive forces between different polymer
chains or segments within polymer chains play a Many polymers, such as polyethylene, have no
large part in determining a polymer’s properties. As permanent dipole. However, attractive forces
mentioned in Section 1.4, atoms can have polarity between polyethylene chains arise from weak
or dipole moments. Since negative charges are forces called Van der Waals forces. Van der Waals
attracted to the opposite positive charges and forces are much weaker than chemical bonds, and
repelled by like charges it is possible to generate random thermal motion around room temperature
attractions that lead to certain structures. can usually overcome or disrupt them.
Molecules can be thought of as being surrounded
by a cloud of negative electrons. But the electrons
1.4.8.1 Hydrogen Bonding are mobile, and at any one instant they might
One of the strongest dipole interactions is the find themselves toward one end of the molecule,
attraction of some oxygen atoms to hydrogen atoms making that end slightly negative (δ2 ). The other
even though they are covalently bonded to other end will be momentarily short of electrons and so
atoms. This is called hydrogen bonding and a sche- becomes (δ1 ). Basically, temporary fluctuating
matic of it using polyamide molecules is shown in dipoles are present in all molecules and the forces
Figure 1.53. The NaH bond provides a dipole due to these dipoles are the basis for Van der
when the hydrogen has a slightly positive charge Waals attraction. Van der Waals forces are quite
and the nitrogen has a slight negative charge. The weak, however, so polyethylene can have a lower
Figure 1.53 Schematic of hydrogen bonding in a pair of polyamide polymer chains [3].
melting temperature compared to other polymers a sample, the number average molecular weight is
that have hydrogen bonding. calculated using Eq. (1.18).
X
Ni Mi
1.4.8.3 Chain Entanglement
Mn 5 X i
(1.18)
Polymer molecules are long chains, which can Ni
become entangled with one another, much like a bowl i
of spaghetti. Along with intermolecular forces, chain where:

entanglement is an important factor contributing to
the physical properties of polymers. The difficulty in I is the number of polymer molecules
untangling their chains makes polymers and the plas-
tic made from them strong and resilient. Ni is the number of molecules that have the
molecular weight Mi.
1.4.9 General Classifications The weight average molecular weight is a differ-

ent calculation as in Eq. (1.19):
Besides the chemical structures of the polymers
in the plastics, there are several other characteriza- X
tions that are important including molecular weight, Ni Mi2
thermoplastics versus thermosets, and crystallinity. Mw 5 X
i
(1.19)
Ni Mi
i
1.4.9.1 Molecular Weight
Figure 1.54 shows a molecular weight distribu-
A polymer’s molecular weight is the sum of the tion chart with the two different molecular weight
atomic weights of individual atoms that comprise a measures noted on it. The ratio Mw /Mn is called the
molecule. It indicates the average length of the molar-mass dispersity index [7] (often called poly-
bulk resin’s polymer chains. All polymer molecules dispersity (PDI)) [7]. If all the polymer chains are
of a particular grade do not all have the exact same exactly the same, then the number average and
molecular weight. There is a range or distribution weight average molecular weights are exactly the
of molecular weights. There are two important same and the PDI is “1.” The larger the molar-mass
but different ways to calculate molecular weight. dispersity index the wider the molecular weight dis-
The most important one is called the number aver- tribution. The molecular weight range can affect
age molecular weight, Mn. For all “i” molecules in many properties of plastic materials.
high-molecular-weight resins offer the ultimate

material performance, being tougher and more
resistant to chemical and environmental attack.
Molecular weight of the polymers that are used
in engineering plastics affects many of the plastics’
properties. While it is not always known exactly
what the molecular weights are, as mentioned
above higher flowing plastics of a given series
of products generally are lower-molecular-weight
polymers.
1.4.9.2 Thermosets Versus

Thermoplastics
A plastic falls into one of the two broad catego-
ries depending on its response to heat: thermoplas-
tics or thermosets. Thermoplastics soften and melt
when heated and harden when cooled. Because of
Figure 1.54 A molecular weight distribution plot this behavior, these resins can be injection molded,
showing number average (Mn) and weight average extruded, or formed via other molding techniques.
(Mw) molecular weights. This behavior also allows production scrap runners
and trimmings to be reground and reused.
Unlike thermoplastics, thermosets react chemi-
Another common means of expressing the length
cally to form cross-links, as described earlier, that
of a polymer chain is the degree of polymerization,
limit chain movement. This network of polymer
this quantifies the average number of monomers
chains tends to degrade, rather than soften, when
incorporated into the polymer chain. The average
exposed to excessive heat. Until recently, thermo-
molecular weight can be determined by several
sets could not be remelted and reused after initial
means, but this subject is beyond the scope of this
curing. Recent advances in recycling have provided
book. Low-molecular-weight polyethylene chains
new methods for remelting and reusing thermoset
have backbones as small as 1000 carbon atoms long.
materials.
Ultrahigh-molecular-weight polyethylene chains can
have 500,000 carbon atoms along their length. Many
plastics are available in a variety of chain lengths, or 1.4.9.3 Crystalline Versus Amorphous
different molecular weight grades. These resins can Thermoplastics are further classified by their
also be classified indirectly by a viscosity value, crystallinity, or the degree of order within the poly-
rather than molecular weight. Within a resin family, mer’s overall structure. As a crystalline resin cools
such as polycarbonate, higher molecular weight from the melt, polymer chains fold or align into
grades have higher melt viscosities. For example, in highly ordered crystalline structures as shown in
the viscosity test for polycarbonate, the melt flow Figure 1.55.
rate ranges from approximately 4 g/10 min for the Some plastics can be completely amorphous or
highest molecular weight, standard grades to more crystalline. Often plastics specifications will report
than 60 g/10 min for lowest molecular weight, high what percentage of it is crystalline (e.g., 73% crys-
flow, specialty grades. tallinity). Generally, polymer chains with bulky
Selecting the correct molecular weight for your side groups cannot form crystalline regions. The
injection molding application generally involves a degree of crystallinity depends upon both the poly-
balance between filling ease and material perfor- mer and the processing technique. Some polymers
mance. If your application has thin-walled sections, such as polyethylene crystallize quickly and reach
a lower molecular weight/lower viscosity grade high levels of crystallinity. Others, such as PET
offers better flow. For normal wall thicknesses, polyester, require slow cooling to crystallize. If
these resins also offer faster mold cycle times and cooled quickly, PET polyester remains amorphous
fewer molded-in stresses. The stiffer flowing, in the final product.
Polymers can often be blended. Occasionally,

blended polymers have properties that exceed those
of either of the constituents. For instance, blends of
polycarbonate resin and PET polyester, originally
created to improve the chemical resistance of poly-
carbonate, actually have fatigue resistance and low
temperature impact resistance superior to either of
the individual polymers.
Sometimes a material is needed that has some of
the properties of one polymer, and some of the
properties of another. Instead of going back into the
lab and trying to synthesize a brand new polymer
with all the properties wanted, two polymers can be
melted together to form a blend, which will hope-
Figure 1.55 Many plastics have crystalline and fully have some properties of both.
amorphous regions. Two polymers that do actually mix well are
polystyrene and polyphenylene oxide. A few other
examples of polymer pairs that will blend are:
Crystalline and amorphous plastics have several
characteristic differences. Amorphous polymers do • PET with polybutylene terephthalate
not have a sharp melting point, but do have what is
• Polymethyl methacrylate with polyvinylidene
called a glass transition temperature, Tg. Glass tran-
fluoride.
sition temperature is discussed in more detail later
in this chapter. A glass transition temperature is the
Phase-separated mixtures are obtained when
temperature at which a polymer changes from hard
one tries to mix most polymers. But strangely
and brittle to soft and pliable. The force to generate
enough, the phase-separated materials often turn
flow in amorphous materials diminishes slowly as
out to be rather useful. They are called immiscible
the temperature rises above the glass transition tem-
blends.
perature. In crystalline resins, the force require-
Polystyrene and polybutadiene are immiscible.
ments diminish quickly as the material is heated
When polystyrene is mixed with a small amount of
above its crystalline melt temperature. Because of
polybutadiene, the two polymers do not blend.
these easier flow characteristics, crystalline resins
The polybutadiene separates from the polystyrene into
have an advantage in filling thin-walled sections of
little spherical blobs. If this mixture is viewed under a
a mold. Crystalline resins generally have superior
high-power microscope something that looks like the
chemical resistance, greater stability at elevated
picture in Figure 1.56 would be seen.
temperatures and better creep resistance.
Multiphase polymer blends are of major
Amorphous plastics typically have better impact
economic importance in the polymer industry.
strength, less mold shrinkage, and less final part
The most common examples involve the impact
warping than crystalline materials. Higher crystal-
modification of a thermoplastic by the microdisper-
linity usually leads to lower permeation rates.
sion of a rubber into a brittle polymer matrix. Most
End-use requirements usually dictate whether an
commercial blends consist of two polymers com-
amorphous or crystalline resin is preferred.
bined with small amounts of a third, compatibiliz-
ing polymer, typically a block or graft copolymer.
Multiphase polymer blends can be easier to pro-
1.5 Plastic Compositions cess than a single polymer with similar properties.
The possible blends from a given set of polymers
Plastics are usually formulated products meaning offer many more physical properties than do the
that they are not always neat polymers. They may individual polymers. This approach has shown
be blends of polymers and they may have many some success but becomes cumbersome when more
additives used to tailor performance properties. than a few components are involved.
Additives often determine the success or failure

of a resin or system in a particular application.
Many common additives are discussed in the fol-
lowing sections. Except for reinforcement fillers,
most additives are added in very small amounts.
1.5.1 Fillers, Reinforcement, and

Composites
Reinforcing fillers can be added in large
amounts. Some plastics may contain as much as
60% reinforcing fillers. Often, fibrous materials,
Figure 1.56 Immiscible blend of polystyrene and such as glass or carbon fibers, are added to resins
polybutadiene. to create reinforced grades with enhanced proper-
ties. For example, adding 30% short glass fibers by
weight to nylon 6 improves creep resistance and
Blending two or more polymers offers yet increases stiffness by 300%. These glass-reinforced
another method of tailoring resins to a specific plastics usually suffer some loss of impact strength
application. Because blends are only physical mix- and ultimate elongation, and are more prone to
tures, the resulting polymer usually has physical warping because of the relatively large difference
and mechanical properties that lie somewhere in mold shrinkage between the flow and cross
between the values of its constituent materials. For flow directions.
instance, an automotive bumper made from a blend Plastics with nonfibrous fillers such as glass
of polycarbonate resin and thermoplastic polyure- spheres or mineral powders generally exhibit higher
thane elastomer gains rigidity from the polycarbon- stiffness characteristics than unfilled resins, but not
ate resin and retains most of the flexibility and as high as fiber-reinforced grades. Resins with par-
paintability of the polyurethane elastomer. For busi- ticulate fillers are less likely to warp and show a
ness machine housings, a blend of polycarbonate decrease in mold shrinkage. Particulate fillers typi-
and ABS (acrylonitrilebutadienestyrene copoly- cally reduce shrinkage by a percentage roughly
mer) resins offers the enhanced performance of equal to the volume percentage of filler in the poly-
polycarbonate flame retardance and ultraviolet mer, an advantage in tight tolerance molding.
(UV) stability at a lower cost. Often reinforced plastics are called composites.
Additional information on the subject of polymer Often, the plastic material containing the reinforce-
blends is available in Refs. [810]. ment is referred to as the matrix. One can envision
The properties of neat polymers are often not ideal a number of ways different reinforcing materials
for production or the end use. When this is the case, might be arranged in a composite. Many of these
materials are added to the polymer to improve the arrangements are shown in Figure 1.57.
performance shortfall. The additives can improve the Particulates, in the form of pigments, to impart
processing and performance of the plastic. For what- color may be added. On occasion particulate, called
ever reason the additive is used, it can affect the per- extender, is added to reduce the amount of rela-
meation, diffusion, and solubility properties. tively expensive polymer used which reduces over-
Additives encompass a wide range of substances all cost.
that aid processing or add value to the final product Platelet additives may impart color and luster,
[11,12]. Found in virtually all plastics, most addi- metallic appearance or a pearlescent effect, but
tives are incorporated into a resin family by the they also can strongly affect permeation properties.
supplier as part of a proprietary package. For exam- Most of these additives have little or no permeation
ple, you can choose standard polycarbonate resin through themselves so when a film contains partic-
grades with additives for improved internal mold ulate additives, the permeating molecule must fol-
release, UV stabilization, and flame retardance; or low a path around the particulate additive as shown
nylon grades with additives to improve impact in Figure 1.58. This is often called a tortuous
performance. path effect.
applications often are rated using an Underwriters

Laboratories rating system. Use these ratings for
comparison purposes only, as they may not accu-
rately represent the hazard present under actual
fire conditions.
1.5.3 Release Agents

External release agents are lubricants, liquids, or
powders, which coat a mold cavity to facilitate part
removal. Internal release agents can accomplish the
same purpose. The identity of the release agent is
rarely disclosed, but frequently they are fine fluoro-
polymer powders, called micropowders, silicone
resins, or waxes.
1.5.4 Slip Additives/Internal

Lubricants
When plastics (particularly films) slide over each
other there is a resistance that is quantified in terms
of the COF. Films with high COF tend to stick
together instead of sliding over one another.
Figure 1.57 Several types of composite materials. Sticking makes the handling, use, and conversion
of films difficult. To overcome sticking, slip agents
are added.
Slip additives can be divided into migrating and
nonmigrating types. Migrating slip additives are
the most common class and they are used above
their solubility limit in the polymer. These types
of additives are molecules that have two distinct
parts, typically pictured as a head and tail as
shown in Figure 1.59. One part of the molecule,
usually the head, is designed to be soluble in the
polymer (particularly when it is molten during
processing) making up the plastic. The other part,
the tail, is insoluble. As the plastic cools and soli-
Figure 1.58 Tortuous path of permeant molecule
difies from its molten state these molecules
through a platelet particulate containing film.
migrate to the surface, where the insoluble end
“sticks up” reducing the COF. This process is
shown in Figure 1.59. These additives are typi-
1.5.2 Combustion Modifiers, Fire, cally fatty acid amides.
Flame Retardants, and Smoke There are migrating slip additives that are not of
this two-part structure. One additive is perfluoro-
Suppressants polyether (PFPE) synthetic oil marketed by
Combustion modifiers are added to polymers to DuPontt under the trademark Fluoroguard®, which
help retard the resulting parts from burning. is an internal lubricant that imparts improved wear
Generally required for electrical and medical hous- and low friction properties. Silicone fluids, such as
ing applications, combustion modifiers and their those made by Dow Corning, can also act as a
amounts vary with the inherent flammability of boundary lubricant. Both of these materials may
the base polymer. Polymers designed for these migrate to the surface of the plastic over time.
Figure 1.59 Mode of action of a typical migrating slip additive.
Some common nonmigrating slip additives

include:
• PTFE (polytetrafluoroethylene) in micropow-

der form imparts the lowest COF of any inter-
nal lubricant. Manufacturers and suppliers
are many including DuPontt Zonyl® and
3M Dyneont.
• Molybdenum disulfide, commonly called
“moly” is a solid lubricant often used in bear-
ing applications.
• Graphite is a solid lubricant used like molyb-
denum disulfide.
Figure 1.60 Antiblock additives maintain film
separation.
1.5.5 Antiblock Additives
Blocking is a surface affect between adjacent 1.5.6 Catalysts
film layers that stick to one another. Blocking is Catalysts, substances that initiate or change the
quantified by the force needed to separate two film rate of a chemical reaction, do not undergo a per-
layers under controlled conditions. Two situations manent change in composition or become part
where blocking is an issue are the opening of blown of the molecular structure of the final product.
film tubes after extrusion and film layer separation Occasionally used to describe a setting agent, hard-
after packing and storage. Antiblock additives are ener, curing agent, promoter, etc., they are added in
used to overcome these issues. minute quantities, typically less than 1%.
Antiblock additives can be divided into two
classes: inorganic and organic. Chemically inert, 1.5.7 Impact Modifiers and
inorganic antiblock additives migrate to the film
surface and partially stick out of the surface to Tougheners
create a microroughness of the film surface. Many plastics do not have sufficient impact resis-
Figure 1.60 illustrates this principle. tance for the use for which they are intended.
The detailed mechanism of how organic anti- Rather than change to a different type of plastic,
block additives work is not yet understood. It is they can be impact modified in order to fulfill the
thought that a barrier layer is formed on the plastic performance in use requirements. Addition of modi-
film surface, thus inhibiting the two adjacent plastic fiers called impact modifiers or tougheners can sig-
film layers’ adhesion. Their usage is limited. nificantly improve impact resistance. This is one of
Organic antiblock additives were partially discussed the most important additives. There are many sup-
above and will not be further mentioned here. pliers and chemical types of these modifiers.
Figure 1.61 Notched Izod of BASF Ultramid® B-3Nylon 6 modified with various levels of Fusabond® N
NM-493D toughener.
General-purpose impact modification is a very 1.5.8 UV/Radiation Stabilizers

low level of impact modification. It improves room
temperature impact strength but does not take into Sunshine and its UV radiation have a deterio-
account any requirements for low temperature rating effect on many polymers. UV stabilizers
(below 0°C) impact strength. For most of these play an important role in plastics for external uses
types of applications only low levels of impact by counteracting the effects of the sun. UV stabi-
modifier will be required (,10%). lizers are used in plastic items such as greenhouse
Low temperature impact strength is required for film, outdoor furniture, and automotive plastic
applications that require a certain level of low tem- parts. The amounts added are very small and
perature flexibility and resistance to break. This is generally less than 1%. Details are available in
for example the case for many applications in the Ref. [13].
appliance area. For this purpose, modifier levels
between 5% and 15% of mostly reactive modifiers 1.5.9 Optical Brighteners
will be necessary. Reactive modifiers can bond Many polymers have a slight yellowish color.
chemically to the base polymer. They can be modified to appear whiter and brighter
Super tough impact strength may be required for by increasing reflected bluish light (in the range of
applications that should not lead to a failure of 400600 nm). One way to accomplish this is by
the part even if hit at low temperatures (2 30°C using an additive that absorbs in the UV range but
to 240°C) under high speed. This requirement can reemits the energy at higher wavelength. This effect
only be fulfilled with high levels (2025%) of is called fluorescence and these types of additives
reactive impact modifier with low glass transition are called optical brighteners or fluorescent whiten-
temperature. ing agents.
Figure 1.61 shows the effect of one toughener on
the Izod performance of a common Nylon 6 plastic.
The toughener used in this graph is DuPont’s 1.5.10 Plasticizers
Fusabond® N MN-493D. The graph shows the Plasticizers are added to help maintain flexibility
improvement in notched Izod performance versus in a plastic. Various phthalates are commonly used
temperature with differing levels of toughener addi- for this purpose. Since they are small molecules
tive. As shown in this figure, the performance can they may extract or leach out of the plastic causing
be dramatically improved. a loss of flexibility with time. Just as deliberately
added small molecules may leach out, small mole- excellent color strength, cost-effectiveness, and UV
cules from the environment may be absorbed by performance and place it as the most widely used
the plastic and act like a plasticizer. The absorption black pigment for thermoplastic applications.
of water by nylons (polyamides) is an example.
Plasticizers increase the space between the 1.5.12 Coupling Agents
polymers.
The purpose of adding fillers is either to lower
the cost of the polymer, make it tougher or stiffer
1.5.11 Pigments, Extenders, or make it flame retardant so that it does not burn
Dyes, and Mica when it is ignited. Often the addition of the filler
Pigments are added to give a plastic color, but will reduce the elongation at break, the flexibility
they may also affect the physical properties. and in many cases the toughness of the polymer
Extenders are usually cheap materials added to because the fillers are added at very high levels.
reduce the cost of plastic resins. Dyes are colorants One reason for the degradation of properties is that
chemically different to pigments. Mica is a special the fillers in most cases are not compatible with the
pigment added to impact sparkle or metallic polymers. The addition of coupling agents can
appearance. Titanium dioxide (TiO2) and carbon improve the compatibility of the filler with the
black are two important pigments that merit further polymer. As a result the polymer will like the filler
discussion. more, the filler will adhere better to the polymer
matrix and the properties of the final mixture (e.g.,
1.5.11.1 Titanium Dioxide elongation, flexibility) will be enhanced.
TiO2 is one of the most important pigments. It is

widely used because it efficiently scatters visible
1.5.13 Thermal Stabilizers
light and absorbs UV light, thereby imparting white- One of the limiting factors in the use of plastics
ness, brightness, and opacity when incorporated into at high temperatures is their tendency to not only
a plastic. TiO2 is commercially available in two crys- become softer but also to thermally degrade.
tal structures—anatase and rutile. Rutile TiO2 pig- Thermal degradation can present an upper limit to
ments are preferred because they scatter light more the service temperature of plastics. Thermal degra-
efficiently, are more stable, and are more durable dation can occur at temperatures much lower than
than anatase pigments. Chalk resistance, retention of those at which mechanical failure is likely to occur.
color (tinted paints) and gloss, and resistance to dis- Plastics can be protected from thermal degradation
coloration by mildew and dirt collection can be influ- by incorporating stabilizers into them. Thermal sta-
enced by TiO2 grade selection. bilizers are discussed in detail in Chapter 2.
Few, if any, commercial grades of TiO2 are pure
TiO2. Most have inorganic and, in some cases, 1.5.14 Antistats
organic treatments deposited on the surfaces of the
Antistatic additives are capable of modifying
TiO2 particles by precipitation, mechanical blend-
properties of plastics in such a way that they become
ing, or via other routes. Unlike colored pigments
antistatic, conductive, and/or improve electromag-
that primarily provide opacity by absorbing visible
netic interference (EMI) shielding. Carbon fibers,
light, TiO2 and other white pigments also provide
conductive carbon powders, and other electrically
opacity by scattering light.
conductive materials are used for this purpose.
When two (organic) substrates rub against each
1.5.11.2 Carbon Black other electrostatic charges can build up. This is
Carbon black describes a group of industrial known as tribocharging. Electrostatic charges can
carbons created through the partial combustion or impact plastic parts in several ways; one of the most
the thermal decomposition of hydrocarbons. Carbon annoying being the attraction of dust particles.
black is unique in that it possesses the smallest One way to counter this effect is to use antistats
particle size and highest oil absorption among (or antistatic additives). This effect is principally a
the commercially available pigments for plastics. surface effect, although one potential counter measure
These characteristics lead to carbon black’s (conductive fillers) converts it into a bulk effect.
Tools that decrease electrostatic charges and 1.6.1 Linear Polymers

hence increase the conductivity of an organic sub-
strate can be classified as: A linear polymer may be considered to be a col-
lection of linear chainlike molecules, such as shown
• External antistat (surface effect) in Figure 1.40. In a solid plastic, a collection of
these linear chains may be arranged in a completely
• Conductive filler (bulk and surface effect) random manner—looped, coiled, and entangled one
• Internal antistat (surface effect). with another. The binding forces holding the atoms
of the polymer chains together are strong primary
An external antistat is applied via a carrier atomic bonds. The discreet polymer chains are
medium to the surface of the plastic part. The same attracted to each another by weaker molecular
considerations and limitations apply as with nonmi- bonds. These weaker bonds may include van der
grating slip additives. Conductive filler is incorpo- Waals’ forces, ionic attractions, and dipole interac-
rated into the organic substrates and builds up a tions, but those concepts are beyond the scope of
conductive network on a molecular level. While this work. But there definitely is attraction between
both approaches are used in organic substrates, they neighboring polymer chains. Creep in a material
are not the most common. such as this involves rupture or interchange of these
An internal antistat is compounded into the molecular bonds under the action of stress, such
organic substrate and migrates to the plastic part that the molecules as a whole or segments of the
surface. The same principal considerations apply as molecules slide past one another, untwist, uncoil,
for migrating slip additives. unravel, or untangle depending on the molecular
The need to protect sensitive electronic components structure and the nature of the stress applied. Not
and computer boards from electrostatic discharge all bonds between one segment and its neighbors
during handling, shipping, and assembly provided the are broken or interchanged at once. Instead the rup-
driving force for development of a different class of tures or interchanges occur in sequence, one action
antistatic packaging materials. These are sophisticated leading to the next. Additionally, the higher the
laminates with very thin metalized films. temperature the less energy is required to cause
There are other additives used in plastics, but the these molecular changes. Creep in plastic materials
ones discussed above are the most common. can be very dependent on temperature and is
always greater at higher temperatures.
A linear polymer may be made less flexible and
1.6 Mechanisms of Creep more creep resistant by the presence of bulky atoms or
side groups of atoms attached periodically along the
of Plastics chain as in PVC, where a large chlorine atom replaces
The mechanisms of creep in plastic materials are one of every four hydrogen atoms. One can imagine it
still generalized and somewhat speculative. That is is easier to untangle a pile of strings or ropes if those
because there has been little published experimental strings do not have bulky side groups such as knots.
or theoretical work in this area. For metals there Figure 1.55 shows a graphic representation of a
has been a little experimental work and much more possible structure of semicrystalline plastic. Each line
theoretical and modeling study. Therefore, the dis- represents a polymer chain. Sections of these polymer
cussion of mechanisms here is based on a chemist’s chains align with sections of other molecules or even
view of what might reasonably occur on the micro- with other sections of the same molecule. These side-
scopic or molecular level. by-side aligned regions are called crystallites. The
The creep mechanism for three classes of plas- weaker bonds described above are the reason for this
tics will be considered: to occur. Crystallization in polymer structures tends to
increase strength and creep resistance.
1. Linear polymers It has also been observed that crystallization in a
polymer may be increased by stretching so that
2. Branched or cross-linked polymers
when this occurs the resistance to further stretching
3. Reinforced plastics. by creep should be increased.
The presence of plasticizers and other additives in reinforcing fibers. Actions probably involved in
a plastic can profoundly affect the creep properties. creep of reinforced plastics are the following:
The effect of plasticizers is to separate the polymer
molecules so that the strength of the secondary bond 1. Gradual straightening of segments of reinfor-
forces between polymer chains is reduced. This pro- cing fibers which requires simultaneous creep
vides a greater degree of mobility in the polymer of the resin binding the fibers in their initial
chains, the tendency to crystallize is greatly reduced, configuration.
and an increased tendency to creep is found. 2. Creep of the resin in regions in which it is
highly stressed in transferring stress from fiber
1.6.2 Branched or Cross-Linked to fiber.
Polymers 3. Gradual rupture of the bond between resin
and fibers with ensuing slip of the released
Thermosetting polymers such as phenol- portion of fibers relative to the resin and
formaldehyde are much more rigid and resistant to other fibers.
creep than linear polymers because of the 3D net-
work formed by strong primary bonds making up 4. In late stages, the reinforcing fibers rupture
the cross-links as shown in Figure 1.40. The small periodically, randomly, and at an increasing
amount of creep that does occur in these types of rate as they become subjected to higher stresses
polymers is probably the result of relative move- for a longer time than they are able to
ments of those segments of the network which are withstand.
not rigidly held by primary bonds but by secondary
bonds. There usually are not many segments held There could be a difference in properties depend-
by the secondary molecular bonds. This mobility is ing upon whether or not there is some organization
exhausted by relatively small creep strains in ten- to the filler such as that shown in the composites
sion, and failure by brittle fracture follows as the discussed previously in Figure 1.57. For filler with
strain increases. a high degree of alignment one would expect dif-
By reducing the density or number of cross-links ferent properties in the direction of the alignment
of some polymers, a balance between some of versus perpendicular to the alignment. Alignment
the desirable features of 3D network polymers can occur during molding operations particularly
(less creep, for example) without some of the unde- for fibrous fillers as alignment can take place dur-
sirable features, such as a tendency for brittleness. ing flow of these plastics into a mold.
Small amounts of cross-linking leave portions of
the chains bound to each other by weak second- 1.6.4 Additives
ary forces but tie them together at other points Additives, besides reinforcing agents, can have an
by strong primary bonds. This results in behavior influence on creep performance. Additives that are
that is similar to that of the 3D network polymer organic small molecules such as plasticizers, some
except that the extent of the mobile regions is flame retardants, UV stabilizers, and release agents
greater, hence greater flexibility and less creep generally increase the amount of creep deformation,
resistance results. all else being equal. These small molecules act like
lubricants between the polymer chains in the plastics,
allowing them to slip past each other more easily.
1.6.3 Reinforced Plastics
Other additives, like pigments and coupling
The creep of reinforced plastics is very primarily agents, can improve creep performance by provid-
influenced by the creep characteristics of the ing a small amount of reinforcement.
reinforcing material. The chief function of the plas-
tic resin is to bind the reinforcing fibers together.
This makes it possible for the reinforced plastic 1.7 Poisson’s Ratio
to function as a unit rather than as a collection of
individual fibers. The polymer/plastic resin serves When a sample of plastic is stretched in one direc-
to distribute the stresses among the individual tion, it tends to get thinner in the other two directions.
Figure 1.62 Specimens subject to tension or compression for determination of Poisson’s ratio.
If it is compressed it would get thicker in the other of springs, beams, plates, cylinders, etc., made of
two directions. Figure 1.62 shows a 3D picture of the metals used at temperatures well below their melt
shape change in tension and the corresponding points is based on classical equations. Those classi-
compression shape change is shown in an alternate 2D cal equations are derived using the relation:
view. Poisson’s ratio, ν, named after Simeon Poisson,
is the ratio of transverse contraction strain (εtrans) to Stress 5 modulus 3 strain
longitudinal (or axial) extension strain (εaxial) in the
direction of stretching or compressing force as in
Eq. (1.20). Tensile deformation is considered positive The classical equations were all derived assuming:
and compressive deformation is considered negative.
The definition of Poisson’s ratio contains a minus sign • The strains are small.
so that normal materials have a positive ratio. For a • The strains are independent of loading rate or
perfectly incompressible material deformed elastically history and are immediately reversible.
at small strains, the Poisson’s ratio would be exactly • The modulus is constant.
0.5. Most practical engineering materials have ν
between 0.0 and 0.5. The theory of isotropic elasticity
• The material is isotropic, that is the material
behaves in the same way in tension and
permits Poisson’s ratios in the range from 21 to 1/2.
compression.
εtrans
ν52 (1.20) This chapter has shown that for plastics, modulus
εaxial
and deformations are dependent on such factors
as the time under load and temperature. While the
The Poisson’s ratio in viscoelastic materials, assumptions listed above may sometimes be justi-
such as elastomers and many plastics, is time fied for plastics, the classical equations cannot be
dependent in the context of transient tests such as used indiscriminately. Each use must be considered
creep and stress relaxation. on a case-by-case basis. Factors such as mode
of deformation, service temperature, fabrication
method, and environment must be considered.
1.8 Using Creep Data in Plastic Several analytical approaches have been used to
Product Design allow for creep and some give very accurate results.
The drawback is that the methods can be quite
The analysis of stress in plastic design is much complex, involving Laplace transforms or numeri-
more complex than design in metal [14]. The design cal methods. These were certainly not attractive to
Figure 1.63 Determination of limiting strain by the secant modulus method.
design engineers before the year 2000. Computer restrictive. In most practical situations, the limiting
software developments have made use of these strain is decided in consultations between the
methods more practically. designer and the material manufacturers.
Once the limiting strain is known, design meth-
ods based on the creep curves are quite straightfor-
1.8.1 Pseudo Elastic Design
ward and the approach is illustrated in examples in
Method Ref. [15].
The pseudo elastic design method has been
widely accepted. Appropriate values of time-
dependent properties, such as modulus, are substi- 1.8.2 Finite Element Analysis
tuted into the classical equations. This approach Complex structures systems are often too compli-
can give sufficient accuracy in most cases if the cated to simply derive relationships between applied
value chosen for the modulus takes into account the loads, deflections, and internal stresses using classi-
service life of the component and the limiting strain cal equations of stress analysis or the pseudo elastic
of the plastic. The limiting strain for the material is design method. A computational/numerical computer
not just a simple value which applies for all plastics tool called Finite Element Analysis can be applied to
or even for one plastic in all applications. It is often model the physical response of a structure to stress,
arbitrarily chosen, although several methods have deformation, or temperature.
been suggested for arriving at a suitable value. One The finite element method was first introduced
method uses a stressstrain plot. The initial tangent in the 1950s. It has been continually developed and
modulus is determined as shown in Figure 1.63. A improved. Although it is a complex technique, the
secant modulus is plotted with a slope that is 85% fundamental principles are relatively uncomplicated.
of the initial tangent modulus. The strain at which Consider a molded part of complex shape. It is
the secant modulus line intersects (at Point “A”) assembled with other parts. One wants to learn if
the stressstrain curve is defined as the limiting the design will function the way it needs to func-
strain. The tangent modulus, also known as tion. One wants to know what are the loads, deflec-
Young’s modulus or the modulus of elasticity, and tions, stresses, and strains the part will experience.
secant modulusstrain curves are often available This information will help determine if the part
from plastics manufacturers. However, for many may fail and perhaps when. Finite element analysis
plastics (particularly crystalline ones) this is too software can help do this.
1.9 Summary
The rest of this book consists of property data on
many plastics and elastomers. Chapters 210 con-
tain multipoint data in the form of plots. The plastics
are grouped by the basic chemical structures of the
plastics. Each of these chapters contains a short
introduction that describes the basic chemical struc-
tures of the plastics in that chapter. The figures that
follow contain the multipoint data. When possible
the graphs will be in groups. All the creep graphs for
“neat” plastics will come first where available.
Impact-modified plastics will follow. Filled plastics
will be presented next. In general, these will be
Figure 1.64 Finite element analysis model grouped by filler type, with a progression to higher
idealization. filler content. Generally, glass fiber will be first, fol-
lowed by other fillers, such as carbon fiber and glass
beads. Many manufacturers often make similar plas-
The first step of any finite element analysis is to tic products. The properties of a similar product
divide the actual geometry of the structure using a from two manufacturers will have similar creep
collection of discrete portions called finite elements. behavior. For instance, a clear PBT resin with 30%
The elements are joined together by shared nodes. glass fiber will have similar creep properties whether
A model idealization is shown in Figure 1.64. The it is made by Ticona, Lanxess, or DuPont.
collection of nodes and finite elements is known as
the mesh. In order to prevent unlimited rigid body
motion, there may also be restraints, which are
fixed in position and cannot move. Loads can be
References
applied to any of the elements. [1] McKeen LW. The effect of temperature and
In a stress analysis problem, the finite element other factors on plastics. Waltham, MA:
software calculates the loads and displacements of William Andrew Publishing; 2008. Plastics
the nodes, and from this information, the stresses Design Library.
and strains in the elements may be calculated. [2] Pilkey WD. Formulas for stress, strain, and struc-
When dealing with metals the stressstrain tural matrices. 2nd ed. Hoboken, NJ; John Wiley
relations are linear unless the metals are at high & Sons; pp. 6376, 4653, 547 55, 2004.
temperature. When using plastics, FEA software Available from: ,http://www.knovel.com/kno-
requires the plastic’s modulus of elasticity. The vel2/Toc.jsp?BookID 5 1429&VerticalID 5 0.
value of modulus of elasticity for plastics is only (accessed 19/7/14).
constant over a very small part of the stressstrain [3] This is a file from the Wikimedia Commons
curve. The software must consider that the modu- which is a freely licensed media file repository.
lus of elasticity changes with strain. Not only does [4] Flexural Creep Modulus in 3 Point Bending for
it change with strain but also changes with time Celcon® M90 and M270 Acetal Copolymer
due to creep. So to find answers to creep problems (MCE 005), Ticona, 2012.
with FEA, the software must have what is called a [5] Wright DC. Environmental stress cracking of
creep model. The model determines strain in terms plastics. Rapra; 1996. pp. 910, 1319.
that drive creep, stress, temperature, and time. The Available from: , http://www.knovel.com/kno-
kind of data usually used by these models is strain vel2/Toc.jsp?BookID 5 409&VerticalID 5 0 .
versus time curves at various stress levels and tem- (accessed 19/7/14).
peratures. The detail of how this is done is beyond [6] Available from: http://en.wikipedia.org/wiki/
this book but is the subject of others [1618]. Dendronized_polymers (accessed 19/7/14).
[7] Stepto RFT. Dispersity in polymer science approach. 1st ed. New York, NY: Springer;
(IUPAC Recommendations 2009). Pure Appl 1993.
Chem 2009;81:3513. [15] Crawford RJ. Plastics engineering. 3rd ed.
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volumes 12. Dordrecht, The Netherlands: Available from: ,http://www.knovel.com/
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[9] Utracki LA. Commercial polymer blends. (accessed 19/7/14).
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1998. method (5th ed.) volume 1: the basis. Woburn,
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1994. 509&VerticalID50. (accessed 19/7/14).
[11] Flick EW. Plastics additives: an industrial [17] Zienkiewicz OC, Taylor RL. Finite element
guide. 2nd ed. Norwich, NY: William Andrew method (5th ed.) volume 2: solid mechanics.
Publishing/Noyes; 1993. Woburn, MA: Elsevier; 2000. Available from:
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1 Introduction to Creep, Polymers,

Plastics and Elastomers

1.1 Introduction by a detailed look at creep, including creep-specific

In this equation, T is the torque and c is the dis-

1.2.4 Flexural or Bending Stress

Figure 1.4 Torsional constants for rods or beams of common geometries.

Figure 1.7 Illustration of hoop stress.

circumferentially. Figure 1.7 shows stresses caused

P 5 the internal pressure

The SI unit for P is Pascal (Pa), while t and r are

There could also be a radial stress especially

b 5 external radius of tube or cylinder

Often the stresses in pipe are combined into a

Failure by fracture in cylindrical vessels is domi-

1.3 Basic Concepts of Creep

Figure 1.11 Strain versus time creep behavior.

point. However, this region concept is commonly

Figure 1.14 Measured creep plots used to construct Figure 1.13.

Figure 1.17 Isochronous creep plot obtained from Figure 1.13.

Figure 1.18 A plane at constant strain slices the stressstraintime plot.

Figure 1.19 Isometric plot obtained from Figure 1.13.

creep strain is the sum of the permanent creep

Figure 1.24 Typical creep rupture curves in air and environment.

of plastic pipes. The superposition technique starts

1.3.2.6 Environmental Stress Cracking These occur without irreversible chemical

Figure 1.33 Three point bending ESC test device

where: tensile stress and the recording of time to rup-

Figure 1.36 Rapra tensile creep machine.

ESC Performance Expectations more prone to ESC than either semicrystal-

Table 1.1 Standard Tests

Measurement ASTM ISO

ethers, ketones, aldehydes, esters, and nitrogen 1.3.2.7 Summary of Creep

Figure 1.38 Addition polymerization.

Figure 1.39 Condensation polymerization.

1.4.2 Copolymers Block copolymer

• Graft copolymer. High-impact polystyrene, or HIPS, is a graft

Figure 1.40 Linear, branched and cross-linked polymers.

Table 1.2 Dipole Moments in Some Small Molecules

Dipole Dipole Dipole

High polarity Nylon 6/6

1.4.6 Steric Hindrance

1.4.7.1 Structural Isomers 1.4.7.2 Geometric Isomers

Figure 1.47 The structure of polypropene.

Figure 1.46 cis- and trans-isomers.

Figure 1.48 The structure of atactic polypropene.

Figure 1.49 The structure of isotactic polypropene.

Figure 1.50 3D ball and stick structure of isotactic polypropene [3].

Figure 1.51 The structure of syndiotactic polypropene.

Figure 1.52 3D ball and stick representation of syndiotactic polypropene [3].

of spaghetti. Along with intermolecular forces, chain where:

1.4.9 General Classifications The weight average molecular weight is a differ-

high-molecular-weight resins offer the ultimate

1.4.9.2 Thermosets Versus

Polymers can often be blended. Occasionally,

Additives often determine the success or failure

1.5.1 Fillers, Reinforcement, and

applications often are rated using an Underwriters

1.5.3 Release Agents

1.5.4 Slip Additives/Internal

Figure 1.59 Mode of action of a typical migrating slip additive.

Some common nonmigrating slip additives

• PTFE (polytetrafluoroethylene) in micropow-

General-purpose impact modification is a very 1.5.8 UV/Radiation Stabilizers