Advanced Course Summary

ADVANCED RUBBER TECHNOLOGY
COURSE SUMMARIES
STUDY GUIDE
This guide is to be used with the online course assignments and textbook:
“Science and Technology of Rubber” 2nd Ed.
Copyright © 1994 - 2006

ADVANCED RUBBER TECHNOLOGY COURSE
SUMMARIES STUDY GUIDE
1 Rubber Elasticity: Basic Concepts and
~ Behavior
ASSIGNMENT NO. 1
I. INTRODUCTION
The basic theory of rubber elasticity accounts for the elastic deformation of rubbery materials.
II. ELASTICITY OF A SINGLE MOLECULE

The long flexible chain molecules necessary for rubbery behavior change their shape
continuously at room temperature. Ordinarily, in the absence of stress, the molecules assume
random configurations. If tensile forces are applied, the molecules take up oriented
conformations. For small deformation, the relation between the applied force, f, and mean end-
to-end distance, r, is f=Ar where A is inversely related to the mean square end-to-end distance of
the unstressed chain.
III. ELASTICITY OF A THREE-DIMENSIONAL NETWORK OF

POLYMER MOLECULES
The number, N, of elastically effective chains per unit volume is the only molecular parameter
which appears in the expression for the strain energy density. Thus, the elastic behavior of a
molecular network under small deformation is predicted to depend only on the number of chains
and not upon their flexibility.
The elastic stresses required to maintain small deformations can be obtained by means of virtual
work considerations, which illustrate that although the constituent chains obey a linear
force/extension relationship (Eq. 1), the network does not.
Copyright Rubber Division, ACS 1994 – 2006

IV. COMPARISON WITH EXPERIMENT

There are several disagreements between theory and experiment. Observed stresses are higher
than predicted, especially at small strains. The Gaussian portion of the measured stresses does not
agree with theoretical results for an ideal network. At large deformations, network chains fail to
obey Gaussian statistics. The theory has proved to be most successful for moderate strains of
about 100-300%.
V. CONTINUUM THEORY OF RUBBER ELASTICITY

In order to obtain a more accurate formulation, it is necessary to use a phenomenological
approach. Such a treatment of the stress-strain behavior of rubbery materials was developed by
Rivlin, who assumed material isotropy in the unstrained state of constant volume. The condition
for isotropy requires that the strain energy density function W, should be symmetrical with
respect to the three principal extension ratios λ1’ λ2’ λ3. Since W is unaltered by a change of
sign of any two of the principal extension ratios, W must depend only on even powers of λ.
Together with the condition for incompressibility (constancy of volume during deformation),
λ1λ2λ3, = I, mathematical treatment will lead to expressions for W or stress-strain relations which
provide a good approximation to the general behavior of rubbery materials.
VI. SECOND-ORDER STRESSES

Stress-strain relations at large strains are non-linear in character. The normal stresses necessary
to maintain a simple shear deformation of amount γ, are predicted to increase in proportion to γ2.
The behavior of rubber under different types of deformation such as torsion and combined
compression and shear is studied.

VII. ELASTIC BEHAVIOR UNDER SMALL DEFORMATIONS

Many rubber products are normally subjected to small deformations, less than 25% in extension
or compression or 75% in simple shear. Elastic analysis can then be applied assuming linear
relationships. The small deformation of a thin rubber block, bonded on its major surfaces to rigid
plates and under compression or extension can be assumed to take place in two stages: a pure
compression or extension of amount e, and a shear deformation. Under tensile loading, a state of
triaxial tension is set up in the central region of the block. Under this condition, cavities (internal
cracks and voids) present in the interior of a bonded block will expand indefinitely at a critical
tensile strain cc. Sudden propagation of internal cracks and voids in bonded rubber blocks have
actually been found to occur at critical strains in good agreement with prediction. To avoid
internal fracture, the tensile stress should be restricted to less than 1/3 of the modulus. In
compression, large stresses can be supported, the limit of which can be calculated by assuming
that the maximum shear deformation should not exceed about 100%.

2 Polymerization
~
ASSIGNMENT NO. 2
I. CLASSIFICATION
Polymerization reactions are classified according to reaction mechanism into functional group (or
step growth) polymerization and chain addition polymerization.
A. Functional Group Polymerization

Here, the chain length increases monotonically with the extent of reaction as molecules
terminating in functional groups react with each other. The kinetics of such reactions are
usually simplified by assuming that the reactivity of a functional group is independent of
the length of the chain to which it is attached. Then the probability of finding a chain x
units long or the mole fraction of x-mers is equal to the product of the probability that the
functional group has reacted (x-1) times, (px-1), and the probability that the last group has
not reacted. (l-p). So Nx (l-p). Very high extents of reaction (p) are necessary to obtain
high molecular weights.
B. Chain Addition Polymerization

In this case, each polymer molecule is formed by a chain reaction initiated by an active
species such as a free radical or ion to which monomer molecules are successively added.
Chain addition polymerization by a free radical mechanism is a typical chain reaction and
includes initiation, propagation and termination stages. Alternative kinetic formulations in
the text result from variation in details of the initiation process. In any case, the overall
rate of polymerization (propagation) depends on the monomer concentration and the square
root of the initiator concentration. The rate of polymerization and the molecular weight of
the polymer are predicted from kinetic analysis. The molecular weight is independent of
the extent of reaction as high polymer is formed and terminated throughout the
polymerization. The molecular weight (molar mass) can be reduced by chain transfer
reactions which terminate the growing chain without altering rate of polymerization.

II. EMULSION POLYMERIZATION

Emulsion polymerization is necessary to produce fast rates of polymerization and high molecular
weights by the free radical chain addition polymerization of dienes to yield synthetic rubber.
The addition of sufficient soap and monomer to water produces a three phase system consisting
of some dissolved soap and monomer in an aqueous phase, large emulsified monomer droplets
and many small soap micelles swollen with monomer. Upon the addition of free radicals
(initiation) to the aqueous phase, polymerization ensues in the micelles which, because of their
small size and large number (about 1018 per cm3), present the largest surface area for free radical
entry. Propagation starts in the micelles converting about one in a thousand of them to monomer
swollen polymer particles. These particles adsorb all of the available soap and replace the
original uninitiated micelles. Propagation continues as free radicals diffuse into the polymer
particles alternately initiating and terminating growing polymer chains. The growing chains are
effectively isolated from one another in the activated particles and can attain high-molecular
weight. Termination is then controlled by the rate of entry of radicals into the polymer particles,
and so both the rate of polymerization and the molecular weight are increased by increasing the
amount of soap.
A. Styrene-Butadiene Rubber (SBR)

The free radical chain addition copolymerization of butadiene and styrene in emulsion is
the most important process for the production of a synthetic rubber. The rate of
crosslinking relative to chain propagation is decreased by reducing the polymerization
temperature enabling the production of high molecular weight SBR without gel and with
superior mechanical properties.
B. Emulsion Polymerization of Chloroprene

Chloroprene polymerizes very rapidly by free radical chain addition in emulsion
preferentially producing a trans-1,4 chain microstructure with sufficient stereoregularity
to show strain-induced crystallization.
III. COPOLYMERIZATION
The composition of a copolymer produced by the simultaneous chain addition polymerization of
two monomers is determined by the relative rate of consumption of each monomer. Reactivity
ratios express the relative rates of "self” and copolymerization of two monomers and relate the
composition of a copolymer to the monomer concentrations. The copolymer formed at different
conversions during the copolymerization of monomers differing in reactivity varies in
composition.

IV. ADDITION POLYMERIZATION by CATIONIC MECHANISM

Here, the active species in a chain addition reaction is cationic and the end of the growing chain
is a carbonium ion (C+). This chain end is associated or paired with a counterion from the initiator
to an extent dependent on the polarity or dielectric constant of the solvent. Typical initiators of
cationic polymerization are strong acids (often Lewis acids) and a cocatalyst which is a hydrogen
donor. Termination is usually a first-order reaction with a large activation energy. The rate of
polymerization depends on the first power of the initiator concentration and on the square of the
monomer concentration. Faster rates of polymerization and higher molecular weights result from
a decrease in temperature.
V. ADDITION POLYMERIZATION BY ANIONIC MECHANISM

Addition polymerization initiated by organometallics proceeds by a chain addition
polymerization with an anionic active center, often a carbanion (C-). The growing carbanion
chain end is coupled with a metal cation to a degree dependent on the nature of the solvent and
cation. Homogeneous anionic polymerizations are amenable to kinetic analysis. Anionic
initiators, such as sodium naphthalene, involve the coupling of a radical-anion to yield a dianion
which initiates a polymer chain at each end. Anionic polymerization often occurs without
termination to produce “living” polymers and a very narrow molecular weight distribution.
Block copolymers may be synthesized by the successive addition of different monomers. The
possibility of propagation by both free carbanions and ion pairs leads to a sensitivity to the nature
of the counterion and the solvent medium. Chain microstructure in the organolithium initiated
polymerization of dienes, and monomer reactivity in the copolymerization of dimes, are affected
markedly by solvent and counterion.
A “coordinate anionic” reaction results from Ziegler-Natta catalysis which involves transition
metal halides and metal alkyls and yields stereospecific polymers. The Cossee “monometallic”
mechanism includes coordination of the monomer at a vacant octahedral position on the
transition metal atom.
VI. GRAFT and BLOCK COPOLYMERIZATION

Graft copolymers are most often prepared by chain addition polymerization onto a polymer
backbone initiated by reaction between free radicals and the polymer chain. Free radicals can
result from chemical initiation, high energy irradiation and mechanical shear. Highly regular
block copolymers can be synthesized by an anionic mechanism. Microphase separation resulting
from the incompatibility of different blocks in triblock polymers has yielded commercial
thermoplastic elastomers consisting of elastomeric chains effectively crosslinked by crystalline
or glassy polymer domains.

3 Structure Characterization in the Science and

Technology of Elastomers
ASSIGNMENT NO. 3
INTRODUCTION
Major objectives of this chapter are: (1) to present in tabular form available characterization
techniques, and principles of their operation, (2) to discuss their utility and pitfalls, and (3) to
discuss the application of certain techniques in the particular area of elastomers.
I. CHEMICAL COMPOSITION AND REPEAT UNIT STRUCTURE

The chemical composition of a polymer is determined by elemental analysis. Spectroscopic
methods are used to determine the way in which these elements are combined. Skeletal bond
vibrations can be detected in the infrared and Raman spectra. The infrared method depends upon
the interaction of infrared electromagnetic radiation with matter resulting in the absorption of
certain wavelengths of radiation, the energy of which corresponds to the energy of transition
between various vibrational states within a polymer. Raman spectra are supplementary to
infrared in that many vibrations which are infrared inactive, are Raman active. Ultraviolet
absorption spectroscopy can be used to detect and estimate the amount of additives and in some
cases can aid in structure determination.
Nuclear magnetic resonance (NMR) spectroscopy is used to detect atoms with magnetic moments
and to determine the local environment. NMR spectroscopy can he used to study the detailed
stereochemical configuration, such as sequence distribution, along a polymer chain, molecular
motion and chain flexibility.
Table I, p. 163, summarizes the characterization techniques.
II. COMPOSITIONAL AND SEQUENCE DISTRIBUTION OF CO-

POLYMERS AND ADDITIVES
An elastomer may be a composite of polymer, additives and impurities or a product incorporating
two or more monomers (copolymer).
To determine whether the elastomer contains additives or impurities, or is heterogeneous itself,

the components of the mixture must be separated. Proper characterization of a polymer requires
8

that a fractionation scheme be capable of separating the polymer on the basis of chemical
composition and molecular weight. Heterogeneity within a sample may result from differences
in the arrangements of monomer units in a particular chain. Chemically different monomer units
may present different structures with different properties.
III. MOLECULAR WEIGHT AND ITS DISTRIBUTION; BRANCHING;

GEL
This section deals with determining molecular weight (MW) averages and molecular weight
distribution (MWD).
Membrane osmometry measures the absolute number average molecular weight (M8). An
osmometer is a device which solvent and polymer solution are separated by a physical barrier (a
membrane) that is designed to permit passage by the solvent only. The tendency of the solvent to
pass through the membrane can be measured as an osmotic pressure, π , which will depend only on
the number of polymer molecules.
The evaluation of light-scattering measurements on polymer solutions yields the weight average
molecular weights (Mw). Mw can also be determined by sedimentation wherein a dissolved
polymer molecule in a solvent of different density, encounters gravitational potential energy
differences when placed in a centrifugal field. For macromolecules, centrifugal fields produce
gradients of concentration which are a function of molecular weight.
The intrinsic viscosity is another parameter which can be related to molecular weight. The
intrinsic viscosity is related to molecular weight by the empirical equation [η] = KMva through
constants K and a which have characteristic values for a given polymer and solvent. K and a are
determined with polymers of known molecular weight.
Gel permeation chromatography (GPC) is a technique for determining MWD. GPC is one of the
routine characterization techniques where it is often necessary to present the data as a full
chromatogram. Such graphs are especially useful for bimodal MWD polymers.
A rapid technique for measuring molecular weight distributions is that of turbidimetric titration. A
dilute solution of the polymer to be characterized is placed in a photometer at constant temperature
with slow stirring, and the turbidity of the solution is recorded continuously as nonsolvent is
added. The higher molecular weight polymer precipitates first and increases the turbidity. As
more nonsolvent is added, additional lower molecular weight polymer precipitates and the
turbidity continues to increase. By calibrating with fractions of known molecular weight, the
relationship between the nonsolvent added and molecular weight is established.
9

LONG-CHAIN BRANCHING. In the early stages of most polymerizations, linear chain

growth predominates. As the conversion increases, chain transfer to dead polymer increases and
branched polymer or gel may be produced. Branching introduces extra chain ends for a given
Mn and thus more network defects. A convenient parameter for denoting the extent of branching,
the ratio of the viscosity of the branched molecule to that of a linear molecule of the same
molecular weight, this is always less than unity. The reduction in molecular size by branching
reduces the intrinsic viscosity, but increases the sedimentation rate of the more compact
molecules. This provides a means for measuring branching in conjunction with GPC and [η].
GEL. Gel is defined as a chemically connected group of molecules which possess properties
“significantly different” from those of simple branched structures. Different properties may be
manifested depending on the macroscopic state of gel. Examination of a polymer containing
microgel by osmometry will yield a proper Mn. By light scattering, if data taken at low scattering
angles, Mw appears infinite. Presence of gels can affect compounding, fabrication, appearance
and strength.
IV. RUBBER-GLASS AND OTHER SECONDARY TRANSITIONS

The relaxation time is a measure of time required for stress relaxation and is a function of
molecular weight distribution, crosslinking, temperature and pressure. The temperature
dependence is empirically correlated by the WLF equation. All polymers shown characteristic
changes in properties as the temperature changed. The glass transition temperature, Tg, is the
temperature at which a rubbery polymer becomes glassy on cooling. Since polymer properties
(mechanical, thermal, optical) are controlled and affected by Tg, they can be used to measure Tg.
V. CRYSTALLINITY
The degree of crystallinity is often described as a weight fraction (Wc) or a volume fraction (fc)
for a two-phase model. Degree of crystallinity can be measured by various techniques. Most
common ones are: specific volume measurements, x-ray diffraction, differential scanning
calorimetry (DSC) and NMR line widths. Classically, the structure of crystal lattices is studied by
x-ray. Because degree of crystallinity in most elastomers is low, it makes determination of crystal
structure very difficult..
Many rubbers contain small to moderate amounts of crystallinity which acts as a reinforcing
tiller. Natural rubber crystallizes significantly when stressed. Polybutadiene and some ethylene-
propylene copolymers possess significant degrees of crystallinity at ambient temperatures.
10

VI. MORPHOLOGY
Most rubber compounds usually are blends of elastomers. It is important to know the
amorphous/ crystalline nature of such blend polymers. In the presence of fillers, their size and
dispersion can have significant effect on physical properties. Rubbers with high Tg will give
higher hardness and modulus compounds. Phases or their distributions are generally studied by
using microscopy, e.g., SEM, TEM.
VII. ENTANGLEMENTS
Polymer molecules entangled with other molecules act like crosslinked material. When heated,
thermal mobility provides faster slips passed each other relieving entanglements. The elastic
response of such materials can be characterized by plateau modulus, GoN which is related to ve,
apparent number of crosslinks:
G n o = v e RT
Good correlations have been obtained for various polymers between curemeter MH and GoN for a
given amount of chemical crosslinks. From this, one can essentially calculate chemical crosslink
contribution to modulus.
11

4 The Molecular Basis of Rubberlike Elasticity

~
ASSIGNMENT NO. 4
I. INTRODUCTION
The rigidity of a material is caused by interatomic and intermolecular forces which produce a
resistance to deformation. The elastic strain limit of solids is very low (-1%), while that of
elastomers may be as large as 1000%. For elastomers, intermolecular forces between chains are
much smaller than intramolecular forces along the chain. Therefore, the thermal motions of
segments of a long chain molecule must be greater in the lateral direction, and the intermolecular
or entropic forces are the major cause of network retraction.
This chapter reviews the early theory of the idealized picture of rubber elasticity including single
chain and network elasticity and affine and phantom networks. More advanced theories of
elasticity are discussed describing the effects of intermolecular entanglements observed in real
networks and phenomenological theories including relations of stress to strain-
swelling-temperature and force-temperature..
II. NETWORK STRUCTURE

A network can be formed by physical or thermoreversible links or by chemical crosslinks. The
perfect network formed from chemical crosslinks is defined introducing cycle rank (ξi junction
functionality, Φ, number of junctioning µ, number of chains υ, and molecular weight of the
chains between two junctions Mc). Limits of network chain length and bimodal networks are
briefly mentioned.
III. ELEMENTARY MOLECULAR THEORIES

A. The Elasticity of a Single Chain
The elasticity of a single chain is determined by its chemical structures, bond angles,
torsional rotational angles and bond length are used to show how different spatial
conformations can be formed. This is represented schematically by a simple polymer
molecule with an instantaneous end to end vector π. A conformational "energy map"
illustrates the isomeric states caused by the stearic repulsive and attractive forces along
the chain. According to statistical mechanical arguments during stretching, the number
of each type of isomeric state remains the same but they redistribute to allow a change in
π. This major part of the elasticity of the chain is referred to as entropic elasticity. The
12

energetic component of elasticity is derived from work done during deformation to

change the relative internal population of isomeric states, the bond angles and the chain
lengths. This should not be confused with deformation carried out at constant volume.
Long chain molecules undergo continuous changes in shape and the number of
conformations that they can assume is very large. Thus, chain dimensions may be
considered only in a statistical sense. The simplest model is an idealized chain consisting
of freely rotating links in which the effects of energetic interactions between different
segments of the chain are ignored.
Assuming moderate extensions for which a simple statistical treatment (Gaussian) is

valid, a probability function expresses the probability that, if one end of a random chain
is fixed at the origin, the other end will be located within an infinitesimal volume
element.
The elastic force of a single chain can be calculated from the number of available
conformations and the thermoelastic phenomena involved in the process and is
proportional to the end-to-end length of the chain (Hooke's Law).
B. Elasticity of the Network

The total elastic free energy of a network relative to an undeformed network can be
obtained by summing the end-to-end vectors of the chains in the deformed network. The
ratios of the mean-squared dimensions used to determine the elastic free energy are
microscopic quantities. To express elastic free energy in terms of the macroscopic state
of deformation two network models have been used, the affine network and the phantom
network.
The junction points in the affine network model are assumed to be embedded in the
network. As a result of this assumption, components of each chain vector transform
linearly with macroscopic deformations.
According to the phantom network model (James and Guth 1947), the junction points
fluctuate over time without being hindered by the presence of the neighboring chains.
The extent of the fluctuations is not affected by the macroscopic state of deformation.
The term phantom derives from the assumed ability of the junctions to fluctuate in spite
of their entanglements with network chains.
13

IV. MORE ADVANCED MOLECULAR THEORIES

The advanced theories take account of entanglement contributions. The theory of rubber
elasticity based on the phantom, affine, and constrained junction models focuses attention on the
junctions.
The constrained-junction model assumes that the fluctuations of junctions are diminished below
those of the phantom network because of the presence of entanglements.
The elastic free energy of the constrained-junction model, similar to that of the slip-link model,
is the sum of the phantom network free energy and that due to the constraints. Both the slip-link
and the constrained-junction model free energies reduce to that of the phantom network model
when the effect of entanglements diminishes to zero. One important difference between the two
models, however, is that the constrained junction model free energy equates to that of the affine
network model in the limit of infinitely strong constraints, whereas the slip-link model free
energy may exceed that for an affine deformation.
The slip-link model incorporates the effects of entanglements along the chain contour into the
elastic free energy. According to the mechanism of the slip link, a link joins two different chains
which may slide along the contour of the chains.
The action of the slip-links are held to be equivalent to additional crosslinks in the networks, but
not with a one-to-one correspondence.
V. PHENOMENOLOGICAL THEORIES
The phenomenological theories of mechanics continuum considers only the observed behavior of
rubber in order to describe experimental stress-strain data. The elastic energy stored in the
system is expressed in terms of principal extension ratios or strain invariants. The stress-strain
relation can then he obtained by differentiation.
VI. THE STRESS-STRAIN-SWELLING-TEMPERATURE RELATIONS

A. Relation of Stress to Strain and Swelling
The stress-strain relations or equations of state are defined by considering the
deformation of a cube from the underformed reference state to the deformed state as
represented by the deformation tensor τ. The elastic free energy expression according to
the widely studied constrained-junction model has been adopted. The equation of state
relating the components of the true stress tensor to deformation is derived from
thermodynamic considerations for simple tension and compression.
14

The true stress is then reduced by the lateral true stress to equal the net force acting along
the X-axis which is used to define the reduced stress [fÌ] or the shear modulus of the
network. The contribution of constraints decreases as the network is stretched or swelled.
The modulus of the dry network decreases with increasing extension due to a decrease in
the constraining action of the surrounding molecules (increase size of fluctuation domain)
on a given molecule and hence is of intermolecular origin. Swollen networks exhibit
lower modulus in that swelling increases the size of the domain of fluctuations of
junctions.
B. Force-Temperature Relations
The determination of the energetic contribution or internal energy of the network to the
total elastic force is derived from thermodynamic considerations equating the
macroscopic energetic component to the macroscopic average of the squared end-to-end
vectors, <π2>. However, experimentally the force must be determined at constant
volume, which is difficult. For this reason, expressions for the force measured at
constant length and pressure are used.
VII. DIRECT DETERMINATION OF MOLECULAR DIMENSIONS

Small angle neutron scattering (SANS) measurements have been used to show that the effect of
swelling and uniaxial extension on chain dimensions is that the transformation of the dimensions
fall between the predictions of the affine and phantom models and that the effect of the state of
dilution during crosslinking on transformation is very pronounced. Fluctuations of junctions
observed with PDMS are substantial equate approximately to those of a phantom network and
the motion of the junctions are diffusive and similar to the Rouse model. Junction motion is
much slower than those of deuterated free chain ends.
15

5 Dynamic Mechanical Properties
~
ASSIGNMENT NO. 5
I. DYNAMIC MECHANICAL PROPERTIES AND VISCOELASTIC

FUNCTIONS
Response to periodically varying strains or stresses (restricted here to small sinusoidal strain or
stress) are defined as dynamic mechanical properties.
A. Storage and Loss Moduli and Compliances

For small deformations in simple shear in which the properties are independent of the
magnitude of deformation (linear viscoelasticity) a sinusoidal strain y produces a stress
which varies sinusoidally, but is out-of-phase with the strain. The stress can be resolved
into a component in-phase with the strain associated with the storage modulus G' (ω) (a
measure of recoverable energy storage and release in the periodic deformation) and
another component 90° out-of-phase associated with the loss modulus G" (ω) (a measure
of the loss of energy as heat).
The strain response to a sinusoidal stress can also be resolved into an in-phase component
associated with the storage compliance J' (ω) and a 90° out-of-phase component
associated with the loss compliance J" (ω) (ratios of strain to stress are called
compliances).1
For small deformations in simple tension, the response is described by a Young's

modulus E' (the ratio of the out-of-phase stress to a practical tensile strain ξ = λ - 1) and
E" (ratio of the out-of-phase stress to strain). The response to a sinusoidal tensile stress is
an out-of-phase strain corresponding to D' and D", the in-phase and out-of-phase
compliances. The ratio G"/G' = J"/J' is tan δ, the loss tangent. Similarly E"/E' = D"/D'
=tan δ.
16

B. Relation to Other Linear Viscoelastic Functions

If a shear is suddenly applied to a linear viscoelastic material, the dependence of the strain
γ(t) on time is expressed as γ(t)=σJ (t). If a shear strain γ is suddenly imposed, the stress
required to maintain this strain is expressed as σ (t) = γG (t).
1
*Please refer to "Introduction to Polymer Viscoelasticity" by John J. Aklonis, William J. MacKnight and Mitchel
Shen. Wiley-Interscience. a division of John Wiley & .Sons. Inc.
J (t) and G (t) arc known as creep compliance and relaxation modulus, respectively. The
linear viscoelastic functions are interrelated.
II. ZONES OF DYNAMIC VISCOELASTIC BEHAVIOR

A logarithmic plot of the viscoelastic functions against frequency reveals regions qualitatively
associated with different molecular responses.
A. The Plateau Zone

In this zone G' changes relatively slowly and G" passes through a minimum. Within this
zone an uncrosslinked polymer behaves somewhat like crosslinked material.
B. The Transition Zone

With increasing frequency, G' and G" increases, with G" increasing faster than G'. This
change is related to the inability of configurational mobility to keep pace with
deformation at short periods of oscillation at high frequency and consequently produces a
higher modulus. Here, the polymer loses its elastomeric quality and appears to he
increasingly stiff as the frequency increases.
C. The Glassy Zone

At very high frequencies, there can be no configurational rearrangements of polymer
chain backbones within the period of oscillation. The strain in response to a given stress
is very small and corresponds to a very high modulus G1 which is characteristic of a hard
glasslike solid. The loss tangent is smaller than in the transition zone.
D. The Terminal Zone

At frequencies below those defining the plateau zone, the period of oscillation is long
enough to allow almost all modes of molecular rearrangement producing a lower
modulus and, at very low frequencies, viscous flow.
17

E. The Equilibrium and Entanglement Zones in Lightly Crosslinked Elastomers

In crosslinked polymers the viscosity becomes infinite and the material acquires an
equilibrium zone.
III. THE TRANSITION ZONE

A. Onset of the Transition Zone; The Monomeric Friction Coefficient
The frequency at the onset of the transition zone ωtr is almost the reciprocal of the
relaxation time Ttr which is a measure of the time required for complete configurational
rearrangement of the segments between two crosslinks or two entanglements. The
monomeric friction coefficient is a measure of the frictional resistance per monomer unit
encountered by a chain segment in translatory motion. The less frictional opposition, the
higher the frequency at the onset of the transition zone.
B. Temperature Dependence of the Friction Coefficient and Dynamic Viscoelastic

Properties
The friction coefficient ζ0 decreases rapidly as temperature increases. A measurement of
G' and G" at an absolute temperature T and frequency ω is equivalent to that at a chosen
reference temperature T0 and ω aT where aT, is the ratio of ζ0 at T and ζ0 at T0. There, on a
logarithmic plot the transition zone will be shifted by a displacement log aT. The
temperature dependence of aT is described by the Williams-Landel-Ferry (WLF)
equation.
C. Free Volume Concept

Amorphous polymers contain empty space around the molecules. Momentary
concentration of this empty space is necessary for molecular rearrangement. Empty
spaces expand linearly with temperature.
D. Dependence of the Friction Coefficient and Dynamic Properties on Pressure.

Plasticizer. Molecular Weight and Crosslinking
1. Pressure. With increasing pressure, P, the free volume decreases and
causes the friction coefficient to increase. The transition zone shifts to lower
frequencies by a shift -log ap on the log ω axis (ap is the ratio of the friction
coefficient at pressure P to the one at P0 =1 atm). A pressure increase of 50
atm has an effect similar to that of a temperature decrease of 1°C.
2. Plasticizer. Plasticizing elastomers usually increase the fractional
18

free volume. The moduli G' and G" will shift along the log ω axis to higher frequencies by log
av (av is the ratio of ζ0 at the given diluent volume fraction to ζ0 of the undiluted polymer).
IV. THE PLATEAU ZONE

A. Uncrosslinked Elastomers
The features of the plateau zone are related to the average spacing between
entanglements along a molecule and the molecular weight. The height of the plateau
zone is independent of molecular weight above a minimum molecular weight. When the
molecular weight is less than the average molecular weight between entanglement points,
the plateau disappears.
B. Crosslinked Elastomers
Some of the entanglements may be trapped during the vulcanization process. When the
entanglements outnumber the crosslinks, the dynamic properties show very large losses at
low frequencies. The abnormal loss is attributed to motions of dangling branched
structures incompletely attached to the network which disentangles.
19

6 Rheological Behavior and Processing of

~ Unvulcanized Rubber
ASSIGNMENT NO. 6
I. INTRODUCTION
The rheological properties and the processing of unvulcanized elastomers are covered in this
chapter. Dr. White's history in the introduction covers, along with rheological properties, quality
control instrumentation, processing and flow simulation processing and has an excellent
bibliography.
II. BASIC CONCEPTS OF MECHANICS

A study of the basic ideas of classical rheological thought is initiated by developing the idea of
the nature of applied forces and the stress tensor. The stress tensor represents the influence of
applied forces on deformations. The stress tensor includes normal stresses (the stresses acting
normal to the surface) and shear stresses (the stresses acting tangential to the surface). The
force-deformation relation can be determined through the solution of the equations of motion
which are the balance of forces at a point within the body.
III. RHEOLOGICAL PROPERTIES

A. Gums.
1. The rheological behavior of unvulcanized elastomers is examined in terms of

viscoelasticity.
2. Experimental Studies.
a. Small Strain Studies.
Studies involving creep and stress relaxation both static and oscillatory can
be represented in terms of Boltzmann's superposition principle. WLF further
interrelates stress relaxation at different temperatures through a temperature-
dependent shift factor aT. T, the relaxation time, G(t) the shear relaxation
modulus and H(T) the shear relaxation spectrum function are interrelated and
influenced by molecular weight and molecular weight distribution (16b).
20

b. Shear viscosity and . normal stresses. Cox and Merg observed that the
non-newtonian shear viscosity function of flexible chain polymers has the
same form as the complex viscosity-frequency function, i.e.,
η (γ) = η* (ω)
The principal normal stress difference, N, when treated as a function of shear

stress was found to be undependent of temperature,
a
N1 = A σ12
3. Theory of Linear Viscoelasticity. Viscoelastic materials have properties which

are intermediate between those of an elastic solid and a viscous liquid. They store
some of the input energy and may recover part of the deformation when the stress
is removed. If both strain and rate of strain are very small, the viscoelastic
behavior is linear and the ratio of stress to strain is only a function of time and not
of stress magnitude.
Viscoelastic behavior was first expressed in analytical form by Maxwell who

suggested that the elastic modulus times the rate of strain should exceed the rate
of increase of stress by an amount proportional to the stress. A more general
pattern of viscoelastic behavior was proposed by Boltzmann in which each
loading step makes an independent contribution to the final stress so that the final
stress can be obtained by the addition of each contribution (Superposition
Principle). (Equation 24).
4. Theory of Nonlinear Viscoelasticity. In developing a theory of non-linear

viscoelasticity valid for large strains, a constitutive equation must be formulated
in a coordinate system embedded in the medium rather than in fixed space and
there is no unique generalization of a constitutive equation to large strain.
B. Compounds
1. Overview. To date, there has been little consensus relative to reasonable

rheological, models; the central thrust of the rheological date is the existence of
yield values and thixotropic characteristics of rubber compounds.
2. Experimental. The yield value and viscosity level increase with both increased
loading and decreased particle size. Stress relaxation following imposed strains in
polystyrene-black compounds does not decay to zero stress, but approximately to
the yield value.
21

The Cox-Merz observation does not apply for dynamic viscosity and complex
viscosity η* (ω) for carbon black filled rubber compounds.
.
η* (ω) is larger than η (γ)
3. Theory of Plastic Viscous Fluids. A three dimensional formulation of the

Bingham plastic is developed by employing a deviatoric stress tensor T in the
basic relationships (10) and (13) and further developed from (56) and (57) to
constitutive equations (64) and (65) for rubber compounds.
4. Plastic Viscoelastic Fluid Models. A material which responds as a viscoelastic

material above its yield point is described mathematically utilizing T and a
memory function H.
5. Thixotropic Plastic Viscoelastic Fluid. Thixotropy is introduced into plastic fluid

behavior by allowing the yield value Y to depend on the history of tr d2 where d is
the rate of deformation tensor.
IV. BOUNDARY CONDITIONS

Slippage occurs between the rubber and viscometer or processing equipment surface and
increases with increase in temperature, but decreases with increase in pressure or surface
roughness. The onset of slippage is independent of metal of construction with exception of
PTFE treated and occurs at approximately 0.2 MPa. However, at low applied pressure, brass and
copper gave the highest shear stresses followed in descending order by aluminum, steel and
PTFE.
V. MECHANOCHEMICAL BEHAVIOR
A. Degradation of Individual Elastomers. Mastication under high shear degrades the
elastomer when chain scission occurs and the free radicals formed are stabilized by the
presence of oxygen. At low temperatures, high shear occurs increasing chain scission
and breakdown. As temperature increases, degradation decreases and will pass
through a minimum and begin to increase again as the rate of oxidative attack
overcomes the influence of the effect of lower shear.
B. Rubber Blends. Graft copolymers can be prepared by masticating in the absence of

oxygen where the free radical chain ends of dissimilar polymers recombine.
C. Elastomers Swollen with Monomers. Free radical chain ends formed by mastication in
the absence of oxygen can also recombine with vinyl monomers to form block
copolymers.
22

VI. RHEOLOGICAL MEASUREMENTS

A. Parallel Plate and Sandwich Rheometer. The simplest type of rheometer involves the
material to be tested sandwiched between two parallel plates. Such an instrument is
practical for elastomers but not for liquids.
B. Biconical Rheometer. The great advantage of the cone plate rheometer is that the
shear rate is constant throughout the sample for small cone angles.
C. Shearing Disk Rheometer. It is related to the parallel disk type shear flow instrument
that has been widely used for polymer solutions and melts.
D. Capillary Rheometer. The application of a cone and plate is limited to low shear rates
or shear stresses below about 10 sec-1 or 105dyn/cm2. The capillary instrument is
applicable to higher shear rates up to 104 sec-1 where the viscosity is relatively
insensitive to molecular weight and its distribution. Capillary rheometers have been
primarily used for quality control.
E. Compression Rheometer. In compression it is assumed that flow is laminar shearing

with the fluid being driven radially outward from the approaching disks. A power law
model is presumed between shear stress and shear rate.
VII. PROCESSING TECHNOLOGY

A. Internal Mixers
1. General. The basic mixer designs are the two counter rotating rolls which rotate
at different speeds (Banbury) and the two counter rotating rolls which are
intermeshing and rotate at the same speed (Shaw). A third type is similar to the
Shaw except the rotors may be moved transverse to their axis to control interrotor
clearance.
2. Basic Studies. Flow visualization studies shows that natural rubber tends to cling
to rotors and most synthetic rubbers are torn into chunks. The chunks disrupt the
incorporation of fillers. The increased surface area associated with chunks
increases the rate of oil absorption. Bale homogenization, black incorporation
and oil absorption were found to be more rapid in the intermeshing rotor mixers.
23

B. Screw Extrusion
1. General. Screw extruders have evolved from the hot feed, deep channel low
length over diameter (L/D) ratio type to the cold feed shallower channel high L/D
pin barrel type.
2. Basic Studies. Flow marker studies have aided in developing new screw and
barrel designs to optimize homogenization and throughput.
C. Die Extrusion
1. General. Die developments include sheeting dies, "T" or coathanger dies to

provide a uniform melt across the die, dies to coextrude two different materials,
dies which extrude curved tubes and profiles and die which orient fibers in the
extrudate circumferentially rather than axially.
2. Basic Studies. Studies have shown that rubber has higher die entrance pressure
losses than thermoplastics. The introduction of fillers reduces die swell and
shrinkage and improves surface quality.
D. Molding
1. Molding includes compression, injection, transfer and blow molding.
VIII. ENGINEERING ANALYSIS OF PROCESSING
• A. Rheology of elastomers is used to determine the source of processing problems which

have arisen from variations in the viscoelastic properties.
B. Dimentional Analysis
1. General. A large recoverable strain represents high viscoelastic forces. The

"Deborah number" represents the ratio of the characteristic relaxation time to the
residence time. The dimensionless groups that need be considered are the
Weissenberg, Deborah and viscoelastic ratio numbers. For a viscoelastic fluid
there will be dynamic similarity between large and small geometrically scaled
isothermal systems only if velocities are scaled with lengths. If any instabilities
or changes occur within such a system, they will occur at a critical value of a
dimensionless group of the form T, U/L, where T , U and L are the time, velocity
and length.
24

2. Rubber Compounds. The dimensionless group for plastic viscous fluids with
yield values is the Bingham number of YL/ηU. It is seen that both viscoelastic
and plastic flow phenomena are associated with dimensionless groups involving
U/L.
3. Non-Isothermal Effects. The Brinkman number, ηU2 / k θ, represents the ability

of the system to conduct heat produced by viscous dissipation and is of great
importance for larger systems where viscous heating will override heat
conduction and the temperature will rise.
C. Simulation of Internal Mixers. Efforts to model flow utilizes one theory presuming
hydrodynamic lubrication theory and a second based on the complete equations of
motion and applying FEA. Basically, it is found that the two rotors act as screw
pumps, pumping in opposite directions and creating a circulation flow in the mixer.
D. Simulations of Screw Extrusion. If we consider the rubber compound to he a plastic

material in the case of no die where the pressure gradient is zero and if the shear stress
is uniform through the screw channel depth, a simple shear flow will arise when the
shear stress exceeds Y. This will set up a pressure gradient induced by the screw
flights and an associated circulation flow will develop. If there is a pressure gradient
due to a die, the shear stress will vary across the channel, reaching a maximum at the
barrel, and low values intermediate within the cross section. If these stresses decrease
below Y, a solid plug will develop at an intermediate position in the cross section.
The flow in pin barrel extruders has been simulated by using hydrodynamic
lubrication theory methods for Newtonian fluids. By embedding a coordinate system
in the screw channel and setting up a flux balance and then solving the resulting
relationships numerically by finite difference methods, computed flow fields in the
neighborhood of pins can be shown.
It is possible to simulate complete velocity and temperature fields through the screw
channel cross sections and not simply be limited to mean fluxes. The resulting
relationships allow evaluation of the effects of the screw flight and pins, but it is a
much more difficult problem to solve.
E. Simulations of Die Extrusion. Calculations to model flow in a die are simplications of

the screw extrusions. In dies there is only pressure now.
Rubber compounds are plastic materials and stresses have low values in the center of
die cross sections. When stresses drop below Y, the velocity gradient will go to zero
and there will be a localized solid plug.
As with the screw extruder, velocity and temperature may be determined through a die
cross section but it is again a difficult problem.
25

7 Vulcanization
~
ASSIGNMENT NO. 7
I. INTRODUCTION
This chapter is an overview of the science and technology of vulcanization. Sulfur-accelerator
vulcanization of NR, SBR. NBR, EPDM and IIR will be discussed. Other curing methods such
as peroxides and phenolic curatives will be discussed. In addition, dynamic vulcanization
process will be discussed.
II. DEFINITION OF VULCANIZATION

Vulcanization is a process of chemically producing crosslinks between polymer chains. The
process is usually carried out by heating the rubber containing curing agents in a mold under
pressure.
III. EFFECT OF VULCANIZATION ON VULCANIZATE PROPERTIES

Crosslinking of elastomer increases modulus and decreases hysteresis. Tensile strength, fatigue
life and toughness increase with increase in crosslink density to a point, then decrease.
IV. CHARACTERIZATION OF VULCANIZATION PROCESS

The vulcanization process is characterized by the use of cure meter at cure temperatures. Scorch
time is taken as the onset of crosslink formation. During curing, torque increases rapidly until
the cure is complete giving a plateau. Further cure may continually increase torque (e.g., for
SBR) or revert (e.g., for NR).
V. SULFUR VULCANIZATION WITHOUT ACCELERATOR

Curing of rubbers with only sulfur takes a long time. For example, 8 phr sulfur, no accelerator
required 5 hours at 140°C for a diene rubber. The addition of ZnO reduced to 1 to 3 hours.
Addition of as low as 0.5 phr accelerator reduced the cure time to only several minutes.
26

VI. ACCELERATED - SULFUR VULCANIZATION

Different types of accelerators increase the rate of vulcanization of sulfur-accelerator systems.
Within a type of accelerator group, differences can be obtained by choosing the individual
accelerators. Fig. 10, p. 352, gives a good schematic of scorch time and cure rates for different
accelerators. In the group of benzothiazolesulfenamides, the scorch resistance and vulcanization
time increase in the order TBBS or CBS, MBS, DCBS.
In accelerated-sulfur cure system, accelerator (Ac) reacts with sulfur to form monomeric
polysulfide of the structure Ac - Sx - Ac. This reacts with rubber to form rubber - Sx - Ac. This
further reacts with rubber to give crosslinks, e.g., rubber - Sx - rubber.
An increase in the concentration of fatty acid, and hence an increase in concentration of available
Zn2+, causes an increased overall rate in the early reactions which lead to the formation of rubber
- Sx - Ac. However, it gives rise to a decrease in the rate of crosslink formation but an increase
in the extent of crosslinking.
Increases in sulfur and accelerator contents increase crosslink densities, and, thus, higher
modulus, stiffness, strength, hardness and lower heat build-up. In natural rubber, as the ratio of
the concentration of an accelerator to the concentration of sulfur increases, the proportion of
monosulfidic crosslinks increases.
The chemistry of S-Ac vulcanization of BR, SBR and EPDM is similar to that of NR. Rubber is
first saturated by accelerator to give Ac - Sx - Ac which gives rubber - Sx - Ac. Only difference
is that in case of MBTS vulcanization, unlike in case of NR, MBT is not eliminated and remains
inextractable because presumably it remains bound to polymer chain.
VII. VULCANIZATION BY PHENOLIC CURATIVES, BENZOQUINONE

DERIVATIVES
Diene rubbers can be vulcanized by the action of phenolic compounds containing -CH2-X groups
where X is an -OH group or a halogen atom. A high diene rubber can also be vulcanized by the
action of a dinitrosobenzene, which forms in-situ by the oxidation of a quinonedioxime which
had been incorporated into rubber along with the oxidizing agent.
Another vulcanizing agent for high diene rubbers is m-phenylenebismaleimide. A catalytic free
radical source such as dicumyl peroxide or MBTS is usually used to initiate the reaction.
27

VIII. VULCANIZATION BY THE ACTION OF METAL OXIDES

Neoprene is cured by metal oxides. The crosslinking agent usually is zinc oxide, which is used
usually along with MgO which is necessary to give scorch resistance. The reaction is thought to
involve allylic chlorine atom which is the result of a small amount of 1, 2 polymerization:
Cl
-CH2 -CH-
CH
CH2
Along with metal oxides, TMTD. DOTG and sulfur are sometimes used for curing neoprene.
This may be desirable for high resilience or for good dimensional stability.
IX. VULCANIZATION BY THE ACTION OF ORGANIC PEROXIDES

Organic peroxides can be used to cure most elastomers. They are, however, more useful for
saturated or low unsaturation polymers. Dicumyl peroxide is widely used; however, its
vulcanizates have the odor of acetophenone, a byproduct of vulcanization process. There are
other peroxides that don't give this odor. Acidic compounding ingredients (fatty acids, certain
carbon blacks, silicas) can catalyze wasteful decomposition of peroxides. Antidegradants can
also reduce crosslinking efficiency by quenching peroxide free radicals.
X. DYNAMIC VULCANIZATION
Dynamic vulcanization is crosslinking of one polymer during its molten-state mixing with
another polymer. Thus, one polymer becomes crosslinked and dispersed in a noncrosslinked
continuous phase. If the disperse phase is elastomeric and the continuous phase is thermoplastic,
the composition can be used as an impact-resistant thermoplastic resin.
28

29

8 Reinforcement of Elastomers by Particulate Fillers

~
ASSIGNMENT NO. 8
I. INTRODUCTION
Reinforcement is a technique for improving mechanical properties. The degree of reinforcement
by a filler depends on the extent of the polymer-filler interaction. Carbon black is the most
effective reinforcing filler known.
II. CARBON BLACK

Carbon blacks are classified according to different manufacturing techniques such as furnace and
thermal processes. The ASTM has also established a classification system for carbon black
based on particle size and degree of surface oxidation.
III. FILLER MORPHOLOGY AND ITS CHARACTERIZATION

Carbon black consists of irregular chainlike branched aggregates of nodular subunits. The filler
morphology is described by two parameters, one related to a mean particle (nodule) size, and one
to structure. The term "structure" describes the extent of intermodular fusion to form aggregates.
Specific surface area can be determined by adsorption methods involving iodine, nitrogen or
large adsorbate molecules.
IV. PHYSICAL AND CHEMICAL INTERACTIONS AT THE FILLER

SURFACE
Carbon black surfaces contain functional groups capable of reacting with polymer molecules to
form grafts during processing and vulcanization. Carbon blacks chemisorb olefins at
vulcanization temperature and the degree of chemisorption is increased in the presence of sulfur.
Carbon black is graphitized when heated to 2700°C or higher. For a carbon black filler rubber,
the stress at 300% extension, the resistance to abrasion and the amount of bound rubber decrease
upon graphitization, while the elongation at break increases and tensile strength is reduced
slightly.
30

V. THE STATE OF FILLER IN THE RUBBER MIX

A necessary condition for reinforcement is that the surface of the filler be wetted by the rubber in
which it is dispersed. When carbon black is mixed into rubber, the penetration of rubber into the
void space in the filler occurs before the carbon black is randomly dispersed. If considerable
rubber-carbon black interaction occurs, bound rubber holds primary aggregates together and
impedes the subsequent dispersion. High-structure carbon blacks generally give the best
dispersion.
VI. THE STATE OF THE RUBBER IN THE FILLER COMPOSITE

The reinforcement of rubber by filler results in some loss of mobility of the chains and, therefore,
affects the physical properties. The severe restriction to motion is confined to a distance of a few
carbon bond lengths along the polymer chain from the surface of a filler particle.
VII. PROPERTIES OF UNVULCANIZED RUBBER-FILLER MIXES

The unvulcanized compounded rubbers containing fillers have a higher viscosity and lower melt
elasticity than the unfilled polymer. The increase in viscosity is greatest at lower shear rates.
High structure blacks give higher extrusion rates and smoother extrudates.
VIII. MECHANICAL BEHAVIOR OF FILLER RUBBER VULCANIZATES

AT SMALL AND MODERATE STRAINS
If a filled vulcanizate is subjected to a periodic sinusoidal shear strains, the dynamic shear
modulus will be a complex quantity, with a component G' in-phase with the strain (the storage
modulus) and component G", 90° out-of-phase (the loss modulus). The variation of storage
modulus with strain amplitude for reinforced rubber containing different amounts of carbon
black indicates that the modulus is large and constant for strain amplitudes up to about 0.001. As
the amplitude is increased, the storage modulus falls until a new plateau value is approached.
The phase angle = G'/G" is small and constant at very small strains. Both G" and tanδ increase
with increasing strain amplitude and pass through maximum values. The storage modulus is
primarily a function of structure, while the difference between storage moduli at low and
moderate double strain amplitude depends only on the specific surface area of the carbon black.
By increasing the average distance between aggregates, the delta storage modulus and tanδ (thus,
the hysteresis) can be reduced. This can be achieved by mixing techniques, coupling agents and
reactive polymer end groups.
The shift factors of carbon black compounds are dependent on frequency as well as on
temperature, therefore, the shift factors are different for the elastic and loss moduli.
31

IX. LARGE DEFORMATION BEHAVIOR

The stress/strain curves at constant rate of strain for a gum vulcanizate (Curve A) p. 408, for a
vulcanizate reinforced with a high surface area carbon black (Curve B) and for a vulcanizate
reinforced with the same black after graphitization (Curve C) are shown in Figure 8. The
deformations are viscoelastic and if the strain rate is reversed the descending stress/strain curve
will fall below the ascending curve. The stress in a filled vulcanizate rises faster than in the
unfilled sample. The inclusion of a rigid filler in a soft matrix will cause the average local strain
in the matrix to exceed the macroscopic strain resulting in a higher stress. On a molecular scale,
adsorption of polymer segments at several sites on a filler particle increases the network chain
density which in turn increases the stress.
When a filled rubber is stretched to a strain ε1, returned to zero strain, and stretched again, the
stress/strain curve lies below the first one, but rejoins it at ε1. The cause of this phenomenon
known as stress softening is attributed to incomplete elastic recovery and the progressive
breaking of network chains attached to filler particles.
X. FAILURE PROPERTIES
The inclusion of particles in a viscoelastic medium increases mechanical energy dissipation.
Fillers do not materially increase the strength of amorphous rubbers near or below the glass
transition, and are most effective in the rubbery region. The fatigue life of carbon black filled
elastomers increases with structure level and decreases with specific surface area. The relative
resistance of various tread compounds to wear depends on the severity of the conditions causing
wear, such as roughness of the abrading surface, slip, normal load and temperature. At high
severity of the abrading conditions, the wear resistance is sensitive to carbon black properties
(structure and surface area), but as conditions become less severe the effect of structure
diminishes.
32

9 The Science of Rubber Compounding

~
ASSIGNMENT NO. 9
I. INTRODUCTION
Compounding is a misnomer for the material science of modifying a polymer or a blend with
other materials to optimize properties to meet a given service application or set of performance
parameters.
II. POLYMERS
A. Natural Rubber
Natural rubber with a world yearly usage of over five million metric tons is the most
widely used elastomer because it improves green strength, adhesion, tear strength and
lowers rolling resistance and heat build up.
B. Synthetic Elastomers
Synthetic Elastomers for tires include emulsion and solution styrene butadiene rubber
(SBR) and polybutadiene (PBD). By varying the microstructure of PBD; i.e., vinyl-1,2,
trans-1,4 and cis-1,4 along with the styrene in SBR, the performance can be dramatically
affected. The variation of the microstructures enables the Tg to be varied and tire
performance to be optimized for wet and dry traction, handling, rolling resistance and
high and low severity tread wear.
Other economically significant elastomers include nitrite rubber (NBR), polychloraprene (CR),
butyl rubber (IIR) and ethylene-propylene diene monomer elastomer (EPDM).
III. FILLER SYSTEMS

A. Carbon Black
Carbon black basics are reviewed in Chapter 8. Empirically, increasing structure results
in improved cut growth and fatigue resistance and decreasing particle size (increasing
surface area) increases abrasion resistance, tear strength, contraction lowers resilience
and increases hysteresis and heat build up.
33

B. Silica and Silicates

The most important fundamental properties of silica are ultimate particle size and extent
of hydration. Fine particle size silica, if silane coupling agents are used, can equal
carbon black performance for reinforcement and tread wear and can improve adhesion,
tear, chip and chunk resistance and lower heat build up.
C. Chemistry of Silane Coupling Agents

Silane coupling agents when used with silicas lowers heat build up and hysteresis.
improves reinforcement, tensile strength and abrasion resistance and serves as a
reversion resistor.
D. Other Filler Systems

Other fillers such as clay, calcium carbonate (whiting) and talc are used because of their
low cost and, along with titanium dioxide, are used in light colored products. The
performance of clay can be enhanced through treatment with silane coupling agents.
IV. STABILIZER SYSTEMS

A. Degradation of Rubber
Resistance to degradation can be improved by one or more of three compound variables;
polymer type, cure system and antidegradant system. Degradation occurs in sulfur cured
systems when the polysulfide crosslink breaks down into monosulfidic crosslinks
causing the compound to stiffen. Other causes are free radical chain scission due to
oxygen and ultraviolet light catalytic oxidation due to heavy transition metals such as
Cu, Mn and Fe, and cracking due to fatigue and ozone.
B. Antidegradant Use
The selection criteria governing antidegradant use involves volatility, solubility,
chemical stability and environmental health and safety.
C. Antidegradant Types
The antidegradant types include the nonstaining antioxidants (phosphites, hindered
phenols, hindered bisphenols and hydroquinones), the staining antioxidants
(polymerized dihydroquinalines and diphenoyl amines), antiozonants (para-phenylene
diamines), and waxes.
34

V. VULCANIZATION SYSTEMS
A. Activators
Activators for sulfur vulcanization are predominately zinc oxide at 2.0 to 5.0 phr and
Stearic Acid at 0.5 to 3.0 phr.
B. Vulcanization Agents
The three predominant vulcanizing agents used are sulfur, insoluble sulfur and peroxides.
C. Accelerators
Accelerators are classified as primary accelerators, ultra accelerator and semi-ultra
accelerators. Synergistic combinations of accelerators are used to optimize cure rates,
reversion resistance and fatigue resistance.
D. Retarders and Antireversion Agents

Retarders are used to increase the induction time of a compound. Antireversion agents
are used to improve the service life of the product.
VI. SPECIAL COMPOUNDING INGREDIENTS

A. Processing Oils
Processing oils serve primarily as a processing aid and for cost reduction. The three
classes of oils aromatic, naphthenic and paraffinic are selected for specific applications
based on the polar groups in the polymer or the solubility of the oil in the polymer and
the tendency for the oil to discolor or migration stain.
B. Plasticizers
Plasticizers other than the processing oil are esters, pine tars and low molecular weight
polyethylene. Polymeric esters are used in high temperature applications where
plasticizer volitity is undesirable. Ester plasticizers lower the Tg of the compound to
improve low temperature properties.
35

C. Chemical Peptizers
Peptizers such as pentachlorothiophenol, phenylhydrazine. dipenhylsulfides and xylol
mercaptan serve as either oxidation catalysts or radical acceptors during mixing which
prevents the polymer from recombining.
D. Resins.
Resins are used to aid processing and /or to tackify rubber. Reactive resins containing
methylol groups can be used as stable vulcanizing agents in the presence of methylene
donors such as hexamethylenetetra amine.
VII. COMPOUND DEVELOPMENT

Initial starting model formulations are obtainable from the literature, raw material suppliers or
independent consultants or consulting laboratories. Further optimization, to meet processing and
product requirements; if minor, may require only a few laboratory and/or factory trials.
However, where complex property targets are to be met, a design of experimental methods such
as Taguchi analysis and multiple regression analysis should also be used.
VIII. COMPOUND PREPARATION

The primary compounding mixer is the batch type internal mixer. The polymer supplier will
furnish model mixing procedures. Further improvement of the mix procedure is essential as a
formulation evolves. Computer monitoring of the mixer variables such as power time and
temperatures will aid in arriving at optimal required batch properties and mix time.
IX. ENVIRONMENTAL REQUIREMENTS IN COMPOUNDING

Health and safety during manufacturing and during the products service life cannot be neglected.
The toxilogical properties of all ingredients, their reaction by-products, and impurities must be
acknowledged and controlled.
36

10 Strength of Elastomers
~
ASSIGNMENT NO. 10
I. INTRODUCTION
Different materials show a tendency to fracture when the stress at the tip of either inherent or
initiated cracks exceed some critical level. The strength of elastomers is considered in terms of
the circumstances of crack initiation and propagation. The effects of the rate of strain and
stress, strain history, temperature and environment are examined with special reference to
rubber.
II. INITIATION OF FRACTURE

A. Flaws and Stress Raisers
Fracture in a solid body starts at internal or external voids or flaws where the stress
concentration is very high and the local stress exceeds a critical value. For elastic solids,
the applied stress at the breaking point (σb ) varies in proportion to 1/l ½, σt, and r½ where
l is the depth of the flaw, σt, is the stress at the crack tip, and r is the radius of the crack
tip. The breaking stress can be measured for specimens containing different notch
length (depth). Then, for an unnotched specimen, the average depth of pre-existing
flaws is found by extrapolating σb/ l curves.
B. Stress and Energy Criteria for Rupture

It has been proposed that fracture occurs at a critical value of the stress intensity factor
(Kc) which is a material characteristic independent of specimen geometry, crack
dimension or loading condition. Kc defined by Kc = π½σb/ l ½ is usually referred to as the
fracture toughness.
An alternative but equivalent fracture criterion is based on an energy balance in which the
amount of energy required to propagate a crack by unit area (Gc) governs fracture. Gc defined
by Gc = πσ2bl/E for a single edge notched specimen is usually referred to as the critical strain
energy release rate.
37

The critical stress intensity factor is then related to the critical strain energy release rate by Kc2 =
EGc, where E is Young's modulus. It is important to recognize that the fracture energy Gc is not
a constant value for a given material; it depends strongly on the temperature and the rate of tear.
III. THRESHOLD STRENGTH AND EXTENSIBILITIES

The minimum fracture energy necessary for crack growth is expressed in terms of molecular
weight between crosslinks. Threshold values of tensile strength and extensibility may be
calculated from the threshold fracture energy and the inherent flaw size.
When about 5 mole % of short chains is combined with long chains, the tensile strength and,
thus, tear strength is considerably higher. This may be due to the result of strain redistribution
within the network.
IV. FRACTURE UNDER MULTIAXIAL STRESSES

Under shear and compression, the fracture develops at 45° to the direction of shear. Under a
uniform triaxial compression, fracture does not occur. Under equibiaxial tension, breaking
stresses have been found to be greater than those in uniaxial tension. Under triaxial tension (P) a
small cavity will expand indefinitely at a finite value of the applied tension given by - Pc = 5E/6
and does not depend much on the strength of the elastomer. In this type of deformation, the
change of potential energy from one state to another is mainly involved.
V. CRACK PROPAGATION
The propagation of cracks is not the same for all elastomers. Three different patterns of crack
propagation can be distinguished:
1. In amorphous elastomers like SBR, the crack propagates at a rate dependent on the
strain energy release rate G and the temperature T.
By comparing the tear energy for different amorphous elastomers, it may be

concluded that the tearing (fracture) energy is the same for all unfilled amorphous elastomers
under conditions of equal segmental mobility. Temperature dependence arises only from
corresponding changes in segmental mobility.
2. The tear strength of strain-crystallized elastomers is increased over a particular range

of tear rates and temperatures at which crystallization occurs. Outside this range, the strength of
the elastomer is associated only with its viscous characteristics.
38

3. The tear strength and tensile strength of an amorphous elastomer are increased by
reinforcement over a specific range of rates and temperatures. This is mostly associated with a
deviation of the tear path and to a lesser extent to an increase in inherent strength.
VI. TENSILE RUPTURE

The tensile strength varies with temperature due to a change in segmental mobility. The tensile
strength rises sharply with an increased rate of elongation to a maximum value at high rates
when the segments do not move and the material breaks as a brittle glass.
The tensile rupture data can also be represented by plotting the breaking stress σb versus the
corresponding extension εb which has a characteristic parabolic shape termed the "failure
envelope". It indicates the maximum breaking elongation for the material which is correlated
with the degree of crosslinking. As the degree of crosslinking is increased, the breaking stress
usually passes through a small maximum due to changes in viscoelastic properties with
crosslinking. Strain-crystallizing elastomers show a rather sudden drop in tensile strength as the
temperature is raised, and this occurs at a critical temperature T, which depends on the degree of
crosslinking.
VII. REPEATED STRESSING: MECHANICAL FATIGUE

It is shown that the fracture energy of elastomers is directly related to the energy dissipated on
stretching almost to the breaking elongation. Fatigue failure is the process in which cracks
appear under repeated tensile loads and propagate in an accelerating way. The number of load
cycles up to failure (fatigue life) for strain crystallizing elastomers has been shown to depend on
a material property, the crack growth constant. For a noncrystallizing elastomer, the fatigue life
prediction has been shown to be quite different and is much more dependent on the size of the
initial crack and the magnitude of the applied deformation.
VIII. SURFACE CRACKING BY OZONE

Stretched samples of unsaturated elastomers develop surface cracks in ozone. Even small cracks
can significantly lower strength and fatigue life. The rate at which crack grows, when the critical
energy condition is met, depends on rate of incidence of ozone at the crack tip and the rate of
segmental motion in the tip region.
IX. ABRASIVE WEAR

When a block of elastomer slides along a hard rough surface under a frictional force, the
elastomer is abraded away at a rate dependent upon the frictional force. The abradability (the
volume abraded away per unit of energy dissipated in sliding and can be represented as A/µ
39

where A is the volume of rubber abraded away per unit normal load and per unit sliding distance
and µ is the coefficient of friction) is found to be somewhat larger for reinforced elastomers, i.e.,
these materials wear away faster under constant frictional conditions.
There are chemical effects in rubber abrasion of unsaturated elastomers. Oxygen imparts
oxidative degradation leading to mechanochemical rupture of bonds. Chemical changes in
rubber can even cause rapid wear of metals. This is attributed to direct chemical attack by
reaction polymeric species, probably free radicals during frictional contact.
40

11 The Chemical Modification of Polymers

~
ASSIGNMENT NO. 11
I. INTRODUCTION
This chapter deals primarily with chemical modifications of polymers which yield rubbers or
elastomers with viscoelastic properties . The subject is too broad to be covered in one chapter
and is therefore covered in outline form with only the more important reactions having been
described. Emphasis is on the principles underlying the chemical modification in specific areas
that the authors feel will be of interest to the rubber chemist and have considerable potential for
further development.
II. ESTERIFICATION, ETHERIFICATION, AND HYDROLYSIS OF

POLYMERS
The chemical modification of polymers is illustrated by the esterification of hydroxyl groups in
cellulose. In view of the expected hydrocarbon shortage and despite its high stiffness and
crystalinity cellulose may soon gain a new role as a polymeric starting material. Synthetic
hydroxy polymers are prepared by complete or partial hydrolysis in a hydrolyzable polymer
such as polyvinyl acetate.
III. THE HYDROGENATION OF POLYMERS

Commercialization of hydrogenated polymers became possible following the introduction of
specific catalysts. Polymers containing butadiene are hydrogenated in solution with a nickel
kieselguhr catalyst but hydrogenation is rarely complete. Kraton G is an example of a
commercially available hydrogenated polymer. The middle block of poly [styrene-butadiene-
styrene (SBS)] is hydrogenated to (SEBS) which exhibits improved thermal and oxidative
properties.
IV. DEHALOGENATION, ELIMINATION, AND HALOGENATION

REACTIONS IN POLYMERS
The dehydrochlorination of poly(vinyl chloride), the discoloration of polyacrylonitrile to
produce cyclized products and the chlorination of polyethylene, ethylene-propylene, and
butadiene styrene copolymers illustrate chemical reactions of polymers.
41

V. OTHER ADDITIVE REACTIONS TO DOUBLE BONDS

A. Ethylene Derivatives
The addition of ethylene derivatives to polydienes is exemplified by the intramolecular
and intermolecular addition of maleic anhydride to polyisoprene.
B. The Prins Reaction

The Prins reaction involves the addition of aldehydic carbonyl groups to polymers with
mainchain unsaturation to introduce hydroxy groups.
VI. OXIDATION REACTIONS OF POLYMERS

Free radical oxidation of unsaturated rubbers lead to epoxidation as well as the formation of
peroxides and hydroperoxides with subsequent chain scission and crosslinking.
VII. FUNCTIONALIZATION OF POLYMERS

Anionically prepared polybutadienes are functionally terminated by active lithium and chain
terminated with benzophenone to dramatically improve the elastomer-filler interaction.
Electrophilic substitution on polystyrene through a chlorometallation reaction yields chlorine
functionality. This has opened up the possibilities of making many derivative of polystyrene.
VIII. BLOCK AND GRAFT COPOLYMERIZATION

A. Effects. Structure. and Properties of Polymers
Block copolymers are macromolecules made up of sequences with different chemical (or
physical; i.e., tactic) structures wherein the sequence is linear such as AAA-BBB. The
branched structure is a graft copolymer.
B. Block Copolymer Synthesis

Block copolymers are synthesized by giving polymerization wherein monomer A is
homopolymerized and then monomer B is added to polymerize further.
Mechanochemical degradation and ionic techniques are mentioned.
C. Examples
Eleven examples of block copolymers containing the three monomer units acrylonitrile,
butadiene and styrene are given. These examples may be prepared by mastication of the
42

polymer or copolymer with monomer or monomers to form the various ABS type
copolymers, some of which occur as a rubber phase dispersed in a resinous matrix.
D. Other Methods of Affecting Mechanicochemical Reactions

Other methods are vibromilling below Tg and chain scission during the extrusion
process.
E. Ionic Mechanisms
Living polymers with an infinite life are possible where carbonions can resume growth
when additional monomer is added. Anionic block copolymerization employs
organolithium initiators which permits precise control over molecular weight and
molecular weight distribution. The processes include the three-stage process with
monofunctional initiators, the two-stage process with difunctional initiators,
monofunctional initiation and coupling, and the formation of tapered block copolymers.
F. Graft Copolymer Synthesis

1. Polymer Transfer
Polymer transfer occurs by free radical chain transfer or free radical monomer
polymerization on an existing polymer. A chain transfer peroxide initiator is added
to a polymer solution abstracting hydrogen and generating free radical on the
polymer chain, and then adding a fresh monomer or polymer solution for grafting
onto these sites.
2. Copolymerization Via Unsaturated Groups

Copolymerization via unsaturated groups occurs by the free radical mechanism as
in number 1 above by adding a free radical initiator or by mastication to form free
radicals and more reactive pendant vinyl groups.
3. Redox Polymerization
Redox polymerization occurs when a metal ion reduces a polymer hydroperoxide
or similar group to a free radical plus an anion. The free radicals on the polymer
backbone act as initiators for graft copolymerization.
4. High-Energy Radiation Techniques

Irradiation of an unsaturated polymer in presence of a vinyl monomer leads to graft
polymerization. Free radicals are formed as irradiation energy is absorbed causing
chain scission and hydrogen abstraction.
5. Photochemical Synthesis
43

With the aid of photosensitizers to speed up the process, graft copolymerization

occurs when ultraviolet light generates free radicals in polymers containing
unsaturation or bromine while in the presence of a monomer.
6. Metallation Using Activated Organolithium Chelating Diamines

Unsaturated elastomers can he readily metallated with activated organolithium
compounds in the presence of chelating diamines or alkoxides of K or Na to form
allylic or benzylic anions as initiator sites to form branched or comb polymer
species.
G. Base Polymer Properties

A graft polymer AB in the presence of the two homopolymers A and B acts as a
compatibilizer to reduce the interfacial energy between the homopolymers and thereby
reduces or prevents macrophase separation.
44

12 Elastomer Blends
~
ASSIGNMENT NO. 12
I. INTRODUCTION
Blending of polymers occurs at various scales in the rubber industry. The relation between
micro-structure and macro-properties is the basis of the Chapter. Polymers are not easily
miscible so that elastomer blends are never truly homogeneous. Blending can optimize
properties (i.e., reach the best compromise), facilitate processing and reduce cost.
II. ELASTOMER/ELASTOMER BLENDS

A. Blending Methods
Latex mixing, solution blending, mechanical blending, mechanochemical blending and
powder mixing are the principle commercial methods for preparing blends. The mixing
process is aided by high temperature and by diluents or suspending media. In latex,
polymers are present as suspended microspheres, and interactions of neighboring spheres
are prevented by the emulsifier. The mixture of two latexes results in a random
suspension of dissimilar particles. Coagulation of a mixture of latexes is also a random
process entirely dependent on soap concentration and not on polymer characteristics. In
solution blending a diluent is added to lower the temperature and shear force requirement
for satisfactory mixing. One polymer usually has a greater affinity for the solvent and the
other will selectively precipitate resulting in macroheterogeneous blends. A combination
of latex and solution blending techniques results in simplification of the polymer
recovery procedures and yields products with better dispersion of filler. With intense
mechanical mixing with roll mills, internal mixers or extruders, blends are produced
which arc macroscopically homogeneous.
B. Characterization of Blends by Physical and Chemical Techniques

Microscopy is used to examine the component parts of a polymer blend. Solubility
differences and optical properties of components have been used to characterize polymer
blends. Dilatometry is used to correlate Tg with chemical structure. Dielectric
relaxation, infrared spectroscopy, nuclear magnetic resonance. X-ray analysis, gas
chromotography, scattering techniques and thermal and thermomechanical methods may
be used to characterize polymer blends.
45

C. Structural Aspects
Phase-contrast microscopy has revealed the presence of discrete domains of each
elastomer in a blend. The study of vulcanizate properties of polymer blends has shown
that physical properties vary with the degree of mixing. The ozone resistance of
SBR/EPDM blends increases as the fineness of dispersion increases. Thermomechanical
techniques have been used to demonstrate the development of interphase crosslinks
during cure.
D. Effect of Blending on Properties

The effect of blending on processing and on cured properties of general purpose
elastomers is discussed.
III. ELASTOMER / PLASTIC BLENDS

A. Physical Mixtures
The glassy and crystalline plastics are being blended into IR and BR to provide
systematic improvements in hardness and reduction of hysteresis. The properties of
butadiene-styrene copolymers differ from polybutadiene/polystyrene blends, in that the
latter showing a linear relation of physical properties with blend composition whereas
the former has a curvilinear relation. Tensile strength of BR/Polystyrene blends is
determined by the blend ratio, whereas hardness, elongation, set and resilience are
determined by the continuity of the glassy phase. The reinforcement of SBR
vulcanizates by polystyrene fillers increases the viscous component of the rubbery
network. Polyethylene acts as a reinforcing agent for IR only when it is chemically
linked to the rubber matrix.
B. Block Copolymers
Block copolymers are a special type of blend. Kraton elastomers consist of ordered block
copolymers of structure S-B-S where S is polystyrene and B is polybutadiene.
Aggregation of polystyrene occurs in the bulk state due to incompatibility with the
butadiene blocks forming glassy particles which act as reinforcing filler. Styrene-
butadiene block copolymers are prepared by homogeneous anionic polymerization. For
low styrene concentrations in a styrene-butadiene block copolymer, a stress-strain
relation similar to uncrosslinked conventional rubbers is produced. As the styrene
concentration increases, the relation approaches that of crosslinked rubbers and
ultimately of styrene homopolymers.
46

The phase morphology of block copolymers in solvents has been studied and a
thermodynamic analysis of the formation of different types of micelles in solution has
been made. The free energy changes required to establish each macrostructural form
have been studied. Observed domain sizes are in agreement with theoretical treatment of
domain size as a function of block length.
C. Polyurethanes
Polyurethanes are composed of block copolymers of flexible segments such as polyether
and polyester and rigid segments such as polyurethane or polyurea. It has been proposed
that these block polyurethanes comprise two interpenetrating semicontinuous phases, one
containing urethane segments and the other rubbery prepolymer segments.
47

13 Thermoplastic Elastomers
~
ASSIGNMENT NO. 13
I. INTRODUCTION
A thermoplastic elastomer (TPE) usually consist of two phases. The soft phase contains a
component which is above its Tg and Tm so that chains are mobile. The hard phase component
is below its Tg or Tm. The relative amounts of two phases control the physical properties of the
TPE's. In this chapter synthesis, morphology and physical and mechanical properties of TPE's
are discussed.
II. SYNTHESIS
Polyurethanes. copolyesters and copolyamides are all produced via condensation
polymerization. As discussed earlier, in condensation polymerization, a molecule containing
two reactive functional groups of one type reacts with another molecule with two reactive
functional groups of another type to form a polymer with a low MW byproduct.
Anionic polymerization produces a narrow MWD TPE compared to condensation

polymerization. An example is triblock copolymers SBS and SIS which are produced under
high vacuum.
Ethylene-propylene copolymers are produced from Ziegler-Natta process. These

polymerizations often produce crystallizable stereospecific products.
III. MORPHOLOGY OF THERMOPLASTIC ELASTOMERS

TPE morphology has a large effect on properties. Generally soft segment is the continuous
phase maintaining the elastomeric behavior. The hard segment is the disperse phase.
Several techniques are used to characterize TPE molecular composition and microstructure.
These are: transmission electron microscopy, infrared spectroscopy, wide-angle x-ray
scattering. small angle x-ray scattering. small angle neutron scattering, NMR and DSC.
48

IV. PROPERTIES AND EFFECT OF STRUCTURE

Stress-softening (Mullins Effect) occurs in most TPE's. If a TPE is strained and released, then
less stress will be required to strain the material a second time. This difference in stress-strain
curves is called hysteresis loop. Fracture of a polymer involves initiation, slow crack growth and
catastrophic crack propagation. The extreme toughness in TPE is due to inhibition of
catastrophic failure from slow crack growth rather than prevention of initiation. The hard
domains in TPE's act as filler and intermolecular points.
The temperature resistance of TPE depends on the chemical structure. The maximum service
temperature is usually about 40°C below the hard segment Tg or Tm. Hysteresis can cause
excessive heat build up so that the local temperature of the material can be much higher than the
nominal temperature. The minimum service temperature is usually about 10°C above soft
segment Tg. Below this temperature, the material will become brittle.
V. THERMODYNAMICS OF PHASE SEPARATION

This section gives a brief description of our current understanding of phase separation in block
copolymers. It also explains how Tg and block lengths of hard segments affect phase
morphology.
Thermodynamic approaches to the size and shape of domains and phase separation have been
developed. It is predicted that phase separation in amorphous block copolymers is favored by
MW of blocks. It was concluded that for AB and ABA block copolymers, morphological
changes should occur at certain ratios of block lengths.
VI. THERMOPLASTIC ELASTOMERS AT SURFACES
The fraction of one component of two phases of TPE's at interface can be significantly different
than the hulk of that component. The presence of an interface can alter the morphology near the
interface. in this section, various analytical techniques are discussed that are used to characterize
surface morphology.
Electron microscopy of surface of cut samples can indicate type of blocks (one or two blocks) at
the surface. It can also show whether lamellae (if present) are oriented parallel or perpendicular
to the surface.
ATR (attenuated total reflectance) has been used to quantify the variation in composition at the
surface in TPE's. ESCA (electron spectroscopy for chemical analysis) is used to quantify the
relative amounts of atomic constituents on the surface of a material giving fractions of each
phase at the interface.
49

VII. RHEOLOGY AND PROCESSING

Processing of TPE depends on the operating conditions and Tg of the soft segment. When
processed above Tg and as temperature is raised, hard segments soften up and become
processable. The viscosity of TPE depends on whether the system is above or below ODT
(order-disorder transition). The processing temperature must be higher than the melting
temperature of hard segment.
VIII. APPLICATIONS
TPE's have replaced conventional elastomers in many areas. These are used either in solution or
in melt which allows their use as adhesives and sealants. SBS are used in shoe soles and as
property modifier for asphalt. TPE's are also very commonly used in ski boots, soccer shoes,
also used is skis and tennis racquets.
50

14 Tire Engineering
~
ASSIGNMENT NO. 14
I. INTRODUCTION
This chapter describes tire construction and tire performance as affected by tire design and tire
materials. It also gives some details on tire manufacturing and tire testing.
II. TIRE TYPES AND PERFORMANCE

Discussion will be concentrated here mostly to radial passenger tires. For rubber-fabric
composite tire is the highest performance requirement rubber product. Therefore, every aspect
of tire (design, material, etc.) is evaluated extensively and thoroughly. Regardless of design or
application of the tire, all tires must meet criteria of key functions such as: load carrying
capacity, driving and braking torque, cornering for handling, steering response and dimensional
stability.
IlI. BASIC TIRE DESIGN

Tires, essentially made of cured rubber composites, have plies of reinforcing cords extending
transversely from bead to bead and is known as carcass. A stiffening belt lies on top of it which
is covered by tread. The belt cords are usually made of steel and have low extensibility and
serve as restriction to carcass ply growth, especially at high speeds. Belt cord angles are usually
between 15°-25°.
IV. TIRE ENGINEERING

The major components of a tire, which govern the performance of a tire, are tread, belt, carcass,
sidewall and bead. This section gives definition of various tire nomenclature and dimensions.
The stiffness of belt affects wear and handling characteristic stability of a tire. The belt stiffness
is a function of the belt angles, wire gauge, belt thickness and compound modulus.
51

The stiffness of a tire belt can be determined by the use of "Gough Stiffness", S, which can be
expressed as:
S=PL3 / 48 EI + 2 PL/8 AG
Where
P is applied force
L supported beam length
E is circumferential modulus of the cord-rubber composite
G is the shear modulus of cord-rubber composite
I is the moment of inertia of the beam
A is the in-plane cross-sectional area.
FEA (finite element analysis) is extensively used to design a tire for optimum performance,
especially for belt and bead stiffness.
V. TIRE MATERIALS
A tire is basically made from a fiber/steel wire/rubber composite. The steel wire and fibers
reinforce the rubber and are the primary load-carrying materials in a tire. A brass plating is
applied to belt wire for better wire-rubber adhesion. The thicker the cord, the stiffer it is.
Thinner cords tend to show better fatigue resistance. Twist increases durability and fatigue
resistance.
Polyester is most commonly used in tires for carcass reinforcement. It is first dipped in a latex
containing resorcinol and formaldehyde to enhance adhesion with rubber and baked before it is
coated with carcass compound in the calendering process.
VI. TIRE TESTING

Tire materials (textiles, wire and compounds) are first tested in a laboratory for quality screening
purposes. The most promising materials are then used to build tires. Then tires are tested on a
test track which simulates various types of actual driving conditions.
52

VII. TIRE MANUFACTURING

Tire compounds are mixed in large Banbury mixers. Compounds are used either in extruders to
get sidewall packages, or in calenders to calender carcass or belt coat compounds. Here each
cord is insulated on all sides with rubber. The finished treatment or calendered cord sheet is cut
to length and angle for tire building.
All tire components are assembled at the tire building machine. Tires are built primarily in two
stages. During tire curing process, the green (uncured) tire is molded into a tire mold. In the
mold, compound flows into the mold shape to give a design to tread and desired thickness to
sidewall.
After curing, tires are inspected visually, and by using x-ray inspection and tire uniformity
machines. After tires pass quality tests, they are stored in the warehouses for shipment.
______________________________________________________________________________
53

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ADVANCED RUBBER TECHNOLOGY

Copyright © 1994 - 2006

1 Rubber Elasticity: Basic Concepts and

II. ELASTICITY OF A SINGLE MOLECULE

III. ELASTICITY OF A THREE-DIMENSIONAL NETWORK OF

Copyright Rubber Division, ACS 1994 – 2006

IV. COMPARISON WITH EXPERIMENT

V. CONTINUUM THEORY OF RUBBER ELASTICITY

VI. SECOND-ORDER STRESSES

Copyright Rubber Division, ACS 1994 – 2006

VII. ELASTIC BEHAVIOR UNDER SMALL DEFORMATIONS

Copyright Rubber Division, ACS 1994 – 2006

A. Functional Group Polymerization

B. Chain Addition Polymerization

Copyright Rubber Division, ACS 1994 – 2006

II. EMULSION POLYMERIZATION

A. Styrene-Butadiene Rubber (SBR)

B. Emulsion Polymerization of Chloroprene

Copyright Rubber Division, ACS 1994 – 2006

IV. ADDITION POLYMERIZATION by CATIONIC MECHANISM

V. ADDITION POLYMERIZATION BY ANIONIC MECHANISM

VI. GRAFT and BLOCK COPOLYMERIZATION

Copyright Rubber Division, ACS 1994 – 2006

3 Structure Characterization in the Science and

I. CHEMICAL COMPOSITION AND REPEAT UNIT STRUCTURE

Table I, p. 163, summarizes the characterization techniques.

II. COMPOSITIONAL AND SEQUENCE DISTRIBUTION OF CO-

To determine whether the elastomer contains additives or impurities, or is heterogeneous itself,

Copyright Rubber Division, ACS 1994 – 2006

III. MOLECULAR WEIGHT AND ITS DISTRIBUTION; BRANCHING;

Copyright Rubber Division, ACS 1994 – 2006

LONG-CHAIN BRANCHING. In the early stages of most polymerizations, linear chain

IV. RUBBER-GLASS AND OTHER SECONDARY TRANSITIONS

Copyright Rubber Division, ACS 1994 – 2006

Copyright Rubber Division, ACS 1994 – 2006

4 The Molecular Basis of Rubberlike Elasticity

II. NETWORK STRUCTURE

III. ELEMENTARY MOLECULAR THEORIES

Copyright Rubber Division, ACS 1994 – 2006

energetic component of elasticity is derived from work done during deformation to

Assuming moderate extensions for which a simple statistical treatment (Gaussian) is

B. Elasticity of the Network

Copyright Rubber Division, ACS 1994 – 2006

IV. MORE ADVANCED MOLECULAR THEORIES

VI. THE STRESS-STRAIN-SWELLING-TEMPERATURE RELATIONS

Copyright Rubber Division, ACS 1994 – 2006

VII. DIRECT DETERMINATION OF MOLECULAR DIMENSIONS

Copyright Rubber Division, ACS 1994 – 2006

5 Dynamic Mechanical Properties

I. DYNAMIC MECHANICAL PROPERTIES AND VISCOELASTIC

A. Storage and Loss Moduli and Compliances

For small deformations in simple tension, the response is described by a Young's

Copyright Rubber Division, ACS 1994 – 2006

B. Relation to Other Linear Viscoelastic Functions

II. ZONES OF DYNAMIC VISCOELASTIC BEHAVIOR

A. The Plateau Zone

B. The Transition Zone

C. The Glassy Zone

D. The Terminal Zone

Copyright Rubber Division, ACS 1994 – 2006

E. The Equilibrium and Entanglement Zones in Lightly Crosslinked Elastomers

III. THE TRANSITION ZONE

B. Temperature Dependence of the Friction Coefficient and Dynamic Viscoelastic

C. Free Volume Concept