Vous êtes sur la page 1sur 95

Chapter 1

INTRODUCTION

Abstract
In this chapter we present an overview on polymer blends,
their classification, thermoplastic elastomers, thermodynamics of
miscibility, different compatibilisation strategies including
dynamic vulcanization, theories of compatibilisation and phase
morphology development. Special attention is given to review the
recent studies and advances related to the system under
consideration. Finally, the scope of the present area of research and
the precise objective of the present topic of research are described.

Chapter 1

In the last few decades the continuous need for materials of high
technological properties has stimulated scientists to develop new classes of
polymers with special properties, which can able to serve in applications
where the usual materials fail. One of the most exciting and rapidly
expanding branches of materials science is in the area of polymers.
Many new multi component polymeric materials have been
developed during the past few decades. The large number of scientific
papers, industrial patents, scientific meetings and exhibitions devoted to
this class of materials is sufficient to witness the strategic importance of
field.
There are a variety of polymers available in the market. However, a
single polymer often cannot achieve the desired properties for industrial
applications. Developing a new polymer with a new chemical structure that
fits the needs of the market is very difficult and costly process. So blending
of polymers is an indispensable for developing new polymeric materials.
Hence new marketable polymer entities are introduced rapidly.
1.1 Polymer Blends
Blending is an art of mixing two or more polymers for getting a
unique property. Polymer blends have played a significant role in the last
few decades in revolutionizing polymer technology, leading to important
and useful applications. The term polymer blend may be defined as a
combination of two or more structurally different polymers or copolymers
giving rise to materials with a range of properties, not delivered by any of
the constituents. Thus, the reason for using blends include the attainment of
specific article performance, by improving the technical properties of the
original polymers, or by adjusting the processing characteristics and
reducing the cost [1-5]. The possibilities of blending of the major polymers

Introduction

are infinite, and the market place will dictate the tailoring of the blends.
Most pairs of polymers are thermodynamically immiscible, but some
polymer blends are compatible and exhibit excellent physical properties
that offer advantages over either of the individual polymers. Sometimes a
third component is added as a compatibiliser, which allows the blending of
the two immiscible polymers.
Polymer blends are made by compounding on mill rolls, in
extruders or in banbury mixtures. Almost all are heterogeneous and consist
of a polymer matrix in which another polymer is embedded. Compatibility
plays an important part in design and optimization of polymer blends.
1.2 Methods of Blending
There are several methods appeared in the literature to make
polymer blends.
1.2.1 Melt blending
Blends can be prepared by melt mixing the ingredients in an internal
mixture. Melt blending avoids contamination and presence of solvent. The
primary disadvantage of melt mixing is the possibility for degradation and
high cost of equipments.
1.2.2 Solution blending
Casting blend from a common solvent is the simplest mixing
method available and is widely practiced. In this method component
polymers are dissolved in a common solvent. In this case there is no chance
of degradation. The main limitation of this method is the incompatible
nature of polymers in many of the commonly used solvents. Residual
solvents can influence the analysis results and is very difficult to make
thick films using this method. Moreover, the waste solvents can cause
environmental problems.

Chapter 1

1.2.3 Latex blending


Emulsion polymerization is employed for the preparation of rubber
toughened plastic blends. The polymers should be in the latex or in the
emulsion form. The mixing process of these micro-sized latex and
subsequent removal of water can produce excellent dispersion and
distribution of discrete phases.
1.2.4 Fine powder mixing
In this method, components are taken in powder form and well
mixed in appropriate ratios.
1.2.5 Mill mixing technique
Very small amount of polymer can be mixed in electrically heated
two-roll mixing mill. The efficiency of a two-roll mixing method can very
from good to very poor depending upon the rheology of the components
and the skill of the operator.
1.2.6 Freeze-drying
A solution of the two polymers is quenched down to a very low
temperature and the solvent is frozen. The polymers will have a little
chance to aggregate and will collect randomly in regions throughout the
frozen solvent. Solvent is removed by sublimation. Freeze drying seems to
work best with solvents having high symmetry.
1.2.7 Chemical and mechanochemical blending
A chemical polyblend is given by polymeric systems in which long
monomeric sequences of one kind is chemically linked to similar
monomeric sequences of different kind either in axial direction or in cross
direction giving block or graft copolymer structures. Selective or random
crosslinking of mechanical blends may ultimately lead to mutual grafting,
cocrosslinking or inter crosslinking resulting in the formation of

Introduction

mechanochemical polyblend often appear as an interpenetrating polymer


network (IPN) of structurally different polymers [6]. Such polymers are
commonly characterized by relatively uniform phase morphology with a
little chance of gross phase separation, improved mechanical strength,
thermal stability, chemical resistance and durability.
Among the different blending techniques, melt blending is more viable.
1.3 Types of Polymer Blends
1.3.1 On the basis of miscibility
Basically there are three different types of blends depending on the
miscibility.
1. Completely miscible blends has got Hm<0 due to specific
interactions. Homogenity is observed at least on a nanometer scale,
if not on the molecular level. This type of blends exhibits only one
glass transition temperature (Tg), which is in between the glass
transition temperatures of the blend components in a close relation
to the blend composition. A well-known example of a blend, which
is miscible over a very wide temperature range and in all
compositions is PS/PPO.
2. In partially miscible blends a small part of one of the blend
component is dissolved in the other part. This type of blend, which
exhibits a fine phase morphology and satisfactory properties, is
referred to as compatible. Both blend phases are homogeneous, and
have their own Tg. Both Tgs are shifted from the values for the pure
blend components towards the Tg of the blend component. An
example is the PC/ABS blends. In these blends, PC and the SAN
phase of ABS partially dissolve in one another. In this case interface
is wide and the interfacial adhesion is good.

Chapter 1

3. Fully immiscible blends have a coarse morphology, sharp interface


and poor adhesion between the blend phases. So these blends are of
no use without compatibilisation. These blends will exhibit different
Tgs corresponding to the Tg of the component polymers. Examples
of fully immiscible blends are PA/ABS, PA/PPO, PA/EPDM and
PA/PP. Now these blends have become commercially successful,
after being efficiently compatibilised using suitable compatibilisers.
1.3.2 On the basis of constituents
On the basis of constituents present in the system, blends are
classified as:
1. Rubber/Rubber blends
2. Plastic/Plastic blends
3. Rubber/Plastic blends
Among these the Rubber/Plastic blends have drawn considerable
attention due to their wide range of properties and applications.
1.4

Thermoplastic Elastomers
Elastomers are really wonderful class of polymers. Crosslinking

makes this all possible. But crosslinked polymers can't be recycled very
easily. So in the interests of keeping the earth from becoming a giant
landfill, researchers have come up with a new approach, the thermoplastic
elastomer. The idea behind thermoplastic elastomers is the notion of a
reversible crosslink.
A thermoplastic elastomer (TPE) is a rubbery material with
properties and functional performance similar to those of a conventional
vulcanized rubber; still it can be processed in a molten state as a
thermoplastic polymer. These are relatively new class of materials, which

Introduction

combine the excellent processibility characteristics of thermoplastics and


the physical properties of elastomers. Among the different types of
polymer blends, TPEs from thermoplastic/rubber blends have gained a lot
of interest recently as they bridge the gap between thermoplastics and
elastomers [7,8]. In these types of blends, the required properties can be
easily achieved by the careful selection of the component polymers and
their blend ratios. Normal crosslinked polymers cannot be recycled because
they don't melt due to the presence of the crosslinks, which tie all the
polymer chains together, making it impossible for the material to flow. The
unique characteristics of TPEs make them very useful and attractive
alternatives for conventional elastomers in a variety of markets such as
automotives, buildings and constructions, wires and cables etc.
There are two main kinds of thermoplastic elastomer, and each has
a different way of keeping its shape and resistance towards temperature
variations. One kind of thermoplastic elastomer is called an ionomer. The
other is called a block copolymer.
An ionomer is a polymer that has a small number of ionic groups
along its backbone chain. A block copolymer is a polymer that has more
than one section, or block.
The main difference between a crosslinked rubber and a
thermoplastic elastomer is that in a crosslinked rubber, the polymer chains
are bonded to each other through covalent bonds. In thermoplastic
elastomers, the polymer chains are held together by bonds, which are
weaker than covalent bonds. In the case of ionomers it is the dipole-dipole
interactions that bind the polymer chains to one another. The block
copolymer uses noncovalent or secondary interactions between the polymer
chains to bind them together. These interactions include hydrogen bonding

Chapter 1

and ionic bonding and other dispersion forces. But in both ionomers and
block copolymers, forces are much weaker than those of the covalent bonds
present in the "crosslinked" polymer chains.
The beauty of using noncovalent interactions to form crosslinks in
TPEs is that when the material is heated, the crosslinks are broken at a
given temperature, which will result in the separation of polymer chains. So
right amount of heat separates the chains from each other. This allows the
material to be processed, and most importantly be recycled. When it is
cooled, the cross links will be reformed.
1.4.1 Advantages of TPEs
(i)

TPEs require little or no compounding since they are fully formulated


and are ready for use as received. It offers rapid, efficient, and
economical means of fabricating rubber articles.

(ii)

Processing of TPEs is cheaper and simpler requiring fewer steps


than does a thermo set rubber. A single step is required to shape
TPEs into finial article, whereas thermoset rubbers require mixing
and vulcanization in addition to the shaping step.

(iii) Processing times for TPEs are shorter since the long cycle time
required for vulcanization is eliminated. Cycle time is typically
seconds instead of the minutes required for thermoset rubbers. This
enhances productivity and reduces costs.
(iv) Being thermoplastic, TPE scrap generated during processing can be
recycled without any loss in functional properties. In contrast,
thermoset elastomers are not recyclable.

Introduction

(v)

As a result of the fewer processing steps and shorter cycle time,


lower energy is consumed in TPE processing than processing of
thermoset rubbers.

(vi) It is easier to obtain finished parts having closer tolerances with


TPEs because of consistent material base and greater ease and
control of processing.
(vii) Elastomers are generally purchased on weight basis but used on
volume basis. Consequently, TPEs offer cost advantages since they
normally have lower specific gravity than thermoset rubbers.
1.4.2 Disadvantages of TPEs
(i)

Most TPEs may require drying before processing.

(ii)

TPEs melt at elevated temperatures; consequently, they are unsuitable


for application requiring even brief exposures to temperatures above
their melting points. Many thermoset rubbers withstand such a short
exposure.

1.4.3 Classification of TPEs


TPEs may be rationally classified into the following categories
according to their chemistry and morphology
(i)

Tri block polymers (Soft) e.g., Styrene-butadiene-styrene (S-B-S) or


styrene-ethylene butylenes-styrene (S-EB-S) etc.

(ii)

Multi block copolymers (Hard) e.g., Thermoplastic polyurethanes


(TPU), Thermoplastic polyamides (TPA) etc.

(iii) Blends of rubbers with thermoplastics and products of dynamic


vulcanization: e.g. Polypropylene (PP)/Ethylene propylene diene
rubber (EPDM) uncrosslinked and partially or fully crosslinked [9-13]

Chapter 1

10

Among these, rubber-plastic blends are the most important category


owing to,
(i)

Ease of preparation

(ii)

Flexibility in the selection of components and composition variation

(iii)

Manipulation of final properties by a judicial control of phase


morphology

(iv)

Possibility of further modification by the introduction of crosslinks


and fillers.
The field of TPEs based on polyolefin rubber/thermoplastic

compositions has grown along two distinctly different product-lines or


classes: One class consists of simple blends and is commonly designated as
thermoplastic elastomeric olefins (TEO) according to ASTM D5593 [14].
In the other class, the rubber phase is dynamically vulcanized, giving rise to
a thermoplastic vulcanizate (TPV) or dynamic vulcanizate (DV) according
to ASTM D 5046 [15].
It is well established that the properties of TPEs derived from
plastic/rubber blends are strongly influenced by the phase morphology. So
a perfect understanding of the phase structure is a pre-requisite for the
development of TPEs. A large number of research papers have been
published on the morphology, rheological properties and mechanical
properties of TPEs [15-31].
1.5 Polymer/Polymer Miscibility
Dobry and Boyer-Kawenoki [32] were the first scientists who
carried out some preliminary experiments on the miscibility of polymers.
Later on Krause did a detailed work on the miscibility of polymers and
published reviews based on the experimental findings [33-35]. A modified

Introduction

11

data on polymer-polymer miscibility has been published by Krause and


Goh [36] for fourth edition of Polymer Handbook in 1999 and upgraded
and reproduced by Utracki [37] in Polymer Blends Handbook in 2002.
The formation of a homogeneous and thermodynamically stable
blend under given temperature and pressure conditions are controlled by
the change in the free energy mixing ie 'Gm. Based on a thermodynamic
viewpoint, miscibility refers to the molecular level homogeneity that
requires the free energy of mixing negative, i.e. 'Gm, should be negative.
Fig.1.1 shows the three possible ways in which the 'Gm of a binary mixture
may vary with composition. In case A, 'Gm is positive over the whole
composition range indicating that the two components are immiscible with
each other to any extent. In the case of B, 'Gm is always negative and thus
the components are completely miscible in all proportions. However, a
negative 'Gm does not assure complete miscibility as case C illustrates. In
the case C, 'Gm shows a negative curvature in the mid composition range,
and thus the mixture can develop an even lower free energy in this range by
splitting into two phases with compositions given by the two minima
resulting in a miscibility gap or partial miscibility.

Change in Free energy

A
B
C

Volume fraction

Figure 1.1: Schematic diagram for the variation of free energy change
with composition in binary polymer mixture.

Chapter 1

12

Thermodynamic miscibility of polymers requires two criteria to be


satisfied at constant temperature and pressure [38]. These include:
'Gm 'H m  T 'S m  0 and
w 2 'Gm

2
wIi T , P

U A

UB

RT
 2B ! 0
I A M A IB M B

(1.1)

(1.2)

in order to ensure stability against phase separation.


where 'H m and 'S m indicate the change in enthalpy and entropy on
mixing respectively, T is the absolute temperature and Ii , Ui and M i are the
volume fraction, density and molecular weight of component i,
respectively.
Equation (1.1) suggests that for spontaneous mixing to occur, 'Gm
must be negative.
However, if two high molecular weight polymers are blended, the
gain in entropy, 'Sm is negligible, and the free energy of mixing can only
be negative if the heat of mixing, Hm, is negative. In other words the
mixing must be exothermic, which requires specific interactions between
the blend components. These interactions may range from strongly ionic to
weak and non-bonding interactions, such as hydrogen bonding, charge
transfer forces, ion-dipole, dipole-dipole and donor-acceptor interactions
etc. Usually, only van der waals interactions occur, which explains why
polymer miscibility is the exception rather than the rule.
The miscibility behaviour of two polymers is strongly depend on
temperature. Each polymer pair is characterized by an interaction
parameter.

Introduction

13

The second thermodynamic requirement given in equation (1.2) is


applicable in the case of partially miscible systems and suggests that the
second derivative of 'Gm with respect to the volume fraction of one of the
components at constant temperature and pressure should be greater than
zero to ensure stability against phase separation since in these systems the
composition fluctuation may lead to phase separation.
The free energy of mixing, 'Gm can be calculated from Flory and
Huggins model [39, 40], according to which
'G M
RT

M i ln M i

i 1

Ni


j 2

j 1

M M
i

F ij

..(1.3)

i 1

where Ni is the number of molecular units, R is the gas constant, and T is


the temperature, as well as the theories of state [41, 42] taking into the
consideration the compressibility of polymer melts. The macromolecular
components in the polymer blends are found to be immiscible due to the
small contribution of entropy to the free energy mixing. Miscibility is an
exception and exists only for very few polymer combinations. The
interaction parameter ij, which can be determined by using solubility
parameter [43], shed light on the miscibility of polymeric components.

F ij

Vo
G i  G j )
RT

(V0= volume)

..(1.4)

Painter et al. [44] showed that the difference in the solubility


parameters ij must be <0.2(J/Cm3)1/2 for mixing to take place on a
molecular level. With increasing GM values, the tendency towards the
phase separation during mixing, which will result in large morphological
units, as shown in the Fig: 1.2 [45].

Chapter 1

14

Figure 1.2: Schematic representation of the changes in the phase character


of polymer blends as a function of their polymer-polymer
interaction energies (From Paul and Bucknall in polymer
Blends vol.1, pp1-14) [Ref.241]

In real melt mixing process, miscible components go through a


mixing state that is characterized by heterogeneity. i.e., a molecular
homogeneous polar system is not inevitable but does depend on the energy
introduced during the mixing as well as the time of the mixing process.
The interface between immiscible polymers in polymer blends can
be schematically represented as in Fig 1.3. The figure shows narrow
interface between two immiscible homopolymers of infinite molecular
weight [46]. The number of contact points between two different polymers
are less in the case of sharp interfacial profile and hence the enthalpic or the
interaction energy contribution to the total free energy is minimized. It is
also clear from the figure that the interaction between the polymer A and B
are very weak.

Introduction

15

Figure 1.3: Interface in immiscible polymer blends (J.Noolandi, Polym.


Eng. Sci. 24, 70, 1984) [Ref: 46]

The above discussions do not mean that immiscible polymer blends


are of little use and that the only solution is to search for miscible ones. In
fact, immiscible polymer blends are much more interesting for commercial
development. Some properties can be achieved only through immiscible
blends. For example impact strength of a polymer cannot be improved
significantly by adding an elastomer miscible to it. It is thus fortune that
most polymer pairs are immiscible. The challenge is to develop processes
or techniques that allow control of both the morphology and interface of
phase separated blends.
1.6 Compatibilisation of Polymer Blends

Compatibilisation is defined as a process of modification of


interfacial properties of phase-separated polymer blends, leading to the
formation of blends having modified interface and/or morphology.
Compatibilisation is the result of a process or technique for improving blend
performance by making blend components less miscible. When two
immiscible polymers are blended without compatibilisation, generally a
mixture with coarse and unstable morphology coupled with poor interfacial
adhesion between the phases is obtained. As a result the blends exhibit
inferior physical properties to those of either individual polymer coupled

Chapter 1

16

with poor structural integrity and heat stability and their performance will be
irreproducible. As mentioned earlier, the high interfacial tension is derived
from the unfavourable interfacial interactions between the individual phase
leads to a large interfacial tension in the melt, which make it difficult to
disperse the components finely enough during mixing and drives phase
rearrangements (coalescence). A poor interfacial adhesion results in an
immature stress transfer, which cannot prevent cracks initiation at the
interface from growing until catastrophic failure occurs. Both theories and
experiments support the role of compatibiliser in multiphase polymer
systems.
1.6.1 Strategies for compatibilisation

There are several methods for the compatibilisation of immiscible


blends. In this chapter, attention is focused only on physical and chemical
compatibilisation techniques.
Compatibilisers are macromolecular species exhibiting interfacial
activities in heterogeneous polymer blends. Usually, the chains of a
compatibiliser have a blocky structure, with one constitutive block miscible
with one blend component and a second block miscible with the other blend
component. These blocky structures can be pre-made and added to the
immiscible polymer blend, but they can also be generated in-situ during the
blending process. The former process is usually referred to as physical
compatibilisation

whereas

the

latter

procedure

is

called

reactive

compatibilisation. The main similarities between reactive and physical


compatibilisation can be described as follows
x

The compatibilising agent is expected to be located at the interface


between the phases.

Introduction

17

Compatibilisation in both types of blending results in particle size


reduction of the dispersed phase enhanced interfacial adhesion
between the phases, and a thermally stable phase morphology during
post-processing steps such as annealing, re-extrusion and injection
moulding.

Both methods of blending allow to design compatibilised blends with


attractive properties.

For industrial purposes melt-extrusion is used as the main


compounding operation for both type of blending.
The role of the compatibilisers in the blending process is firstly to

retard the formation of the Rayleigh disturbances on the generated threads of


polymer, as result of decreased interfacial tension. The lower the interfacial
tension, the smaller the diameter of the thread consequently, the smaller the
size of the generated droplets of the polymer will be.
The research group of Thomas and co-workers have extensively
studied the compatibilisation of immiscible polymer systems. They have
performed either physical or reactive compatibilisation techniques on a series
of multiphase blends such as NR/PS [47-51], NR/PMMA [52-57],
PS/PMMA [58] PP/(acrylonitrile-co-butadiene) rubber (NBR) [59-63],
PS/NBR [64], high density PE (HDPE)/NBR [65-68], PS/polybutadiene (PB)
[69,70], PA/NBR [71,72], PA/PS [73,74], PE/polyethylene-co-vinyl acetate
(EVA) [75-78], PA/EPR [79-81], PE/PP [82,83], PA/PP [84,85] and
polytrimethylene
(PTT/EPDM) [86].

terephthalate/ethylene

propylene

diene

terpolymer

Chapter 1

18

1.6.1.1 Physical compatibilisation

Physical

compatibilisation

is

the

classical

approach

to

compatibilising immiscible polymer blends. In this, the compatibilising


agent is chemically synthesized prior to the blending operation, and
subsequently added to the blend components as a non-reactive component.
The well-selected copolymer bearing two distinct segments will be located
preferentially at the interface owing to its chemical and molecular
characteristics. Each segment will penetrate to the phase with which it has
specific affinity. This will reduce the interfacial tension between the blend
components enhance the interfacial adhesion, and promotes adhesion
between the phases [87-90]. However this approach inherently bears two
major limitations.
x

Compatibilisation of each immiscible polymer blend needs a


specific block or graft copolymer. Consequently, a particular
synthetic procedure is required to obtain the copolymer. This is
often tedious and costly.

The amount of copolymer to be added is higher than required to


saturate the interface. This is because for thermodynamic and
thermo mechanical reasons, a portion of the copolymer introduced
may never reach the interfaces. In order to reach the copolymer at
the interfaces during melt blending, it has to undergo successively,
melting and plastification, dispersion, solubilization and molecular
diffusion respectively. These steps will depend on the molecular
architecture of the copolymer and mixing. Thus, getting the
compatibiliser at the interface is a major problem facing physical
compatibilisation [91].

Introduction

19

The interfacial situation of an immiscible polymer blends in the


presence and absence of a pre-made copolymer is presented in Fig. 1.4.

(a)

(b)

Figure 1.4: Interfacial situation of an immiscible polymer blend in the (a)


absence and (b) presence of a copolymer. Figure 1.14a
illustrates the lack of entanglement between the two polymers
at the interface results in a material with poor macroscopic
properties where as Figure 1.14b demonstrates the way by
which the polymer interface is strengthened by a surfactant.

The pioneering studies in this area have been reported by Molau


[92-94], Riess et al. [95-98] Gaillard et al. [99], Inoue et al. [100], Fayt and
coworkers [101-107], Heikens and coworkers [108,109] and Paul and
coworkers [110-112].
Molue et al. [92-94] clearly demonstrated the ability of block
copolymers to emulsify polymer dispersion in solution and thus inhibit
phase separation. Reiss et al. [95-98] found that block copolymers are more
effective than graft copolymers in increasing the compatibility of
PS/PMMA and PS/IIR. Gaillard et al. [99] examined the surface activity of
copolymers by studying the interfacial tension reduction in mixed polymer
solutions. Inoue et al. [100] reported the mechanism of domain formation
on a ternary system consisting of PS/Polystyrene-b-polyisoprene /
polyisoprene (PS/PS-g-IIR/IIR). Fayt and coworkers [101-107] observed a
significant reduction in the dispersed phase size and an increase in the

Chapter 1

20

interfacial adhesion as a result of melt blending PE and PS with 2% of


block copolymer. They have also showed that the copolymer is uniformly
absorbed at the interface between the two polymers.
Recently Sores et al. [113] reported on the compatibilisation of
elastomer blends based on EPDM using different functional rubbers and
investigated the compatibilising efficiency in terms of mechanical
properties and swelling degrees. Maleic anhydride, mercapto, epoxy and
oxazoline functionalised rubbers were used as compatibilisers.
1.6.1.1.1 Factors affecting the efficiency of physical compatibilisation

The choice of block or graft copolymer as compatibilising agent is


based on the miscibility of its segments with the components of the blends.
For a copolymer to be effective, it must locate at the interface between the
immiscible phases. A schematic representation of the supposed
conformation of a triblock, diblock, multigrafted and single grafted
copolymers at the interface of the heterogeneous polymer blends are given
in the Fig.1.5. The simpler the chain microstructure of the copolymer, the
easier is the penetration of the segments in the respective blend phases will
be. The factors affecting the efficiency of the compatibilisers are:
x

Chemical nature of the compatibilisers

Copolymer length and sequence of distribution (symmetry)

Molecular weight and composition of the copolymer

Concentration of the copolymer

Location of the copolymer in the blend

Viscosity of the compatibilisers

Introduction

Interaction parameter balance and heat of mixing

Blending conditions

Order of addition of the compatibiliser

21

Figure 1.5: Schematic picture of conformations for diblock, triblock,


multigraft, singlegraft copolymers at the interface of a
heterogeneous polymer blend
1.6.1.2 Reactive compatibilisation

Reactive compatibilisation is one of the most important costeffective mixing technique by which one can generate new multiphase
polymeric systems with stable and controlled morphologies. The reactive
compatibilisation technique has several advantages over physical
compatibilisation. During reactive blending the interfacial chemical
reaction gives raise to in-situ formed copolymers, which suppress the
coalescences and reduce the interfacial tension. As a result of this, a stable
and a fine morphology is obtained with enhanced interfacial adhesion
between the phases. Additionally most of these reactions are very fast and,
they can be performed with in the time scale of an industrial extruder.
The reactive polymers may be obtained by polymerization through
terminal, backbone and side chain groups by copolymerisation of
monomers containing the desired reactive groups, and by chemical
modification of pre-formed polymers using free radical grafting,

Chapter 1

22

substitution, terminal modification etc. There are three main scenarios for
reactive compatibilisation of two immiscible polymers.
1. The base polymer components are mutually reactive. In this case
reactive compatibilisation is straightforward. The reaction between
them at the interfaces will lead to the formation of a copolymer.
2. One polymer bears potentially reactive groups and other is
chemically inert with respect to them. Reactively compatibilising
them requires that the non-reactive polymer be functionalized with
functional groups that can react with the reactive one. An alternative
is to introduce a reactive polymer that is miscible with the nonreactive polymer and can react the reactive one.
3. Neither of the base polymers contain reactive group. In such cases,
different compatibilisation methods can be used. The first one is to
add two reactive polymers that are mutually reactive and miscible
with component polymers. The second one is to fuctionalize
component polymers with different functional groups, which are
mutually reactive.
1.6.1.2.1 Advantages of reactive compatibilisation

In reactive compatibilisation chemical reactions are involved in the


blending process. This makes reactive compatibilisation very
attractive and cost effective.

It offers the possibility of generating compatibilisers during melt


blending directly at the interfaces between the base polymer
components with out separate synthetic and purification steps.

Introduction

23

The formation of the copolymer at the polymer-polymer interface,


where it is needed most, directly during the melt blending, leads to
the significant reduction in the particle size and significant
reinforcement of the interfacial toughness.

Some times the desired compatibilisers cannot be synthesized


separately by existing synthetic procedures. Reactive compatibilisation
then becomes the method of choice. The functionalization of existing
polymers in the melt can now be done in a polymer processing
machine.

The main advantage of the reactive blending technique to some


commercial organizations is that the process can be conducted in
different ways with different property outcomes. Thus, the product
cannot be de-engineered by analysis, which provides an element of
secrecy to the manufacture.

1.6.1.2.2 Types of compatibilising reactions

Reactive polymers undergo the usual chemical reactions seen in low


molecular weight materials. The reactivity of a functional group does not
depend on the size of the molecule to which it is attached. But the steric
hindrance to the reaction sites by polymer backbone reduces the reaction
rate [114]. In melt blending the reaction rate can also be reduced by the
restricted diffusional mobility of the functional groups. In order to achieve
successful compatibilisation of polymer blends, the polymers must have
sufficiently reactive functional groups, the reaction should be fast,
selective, and preferably irreversible; and mixing conditions should be such
as to minimize mass transfer limitations to reaction.

Chapter 1

24

Reactive polymers are classified into eight major categories


according to the types of reactive functionalities and characteristics of the
compatibilisation reactions namely
x

Maleic anhydride

Carboxylic acids

Reactive group capable of interchange reactions

Primary and secondary amines

Hydroxyl groups

Heterocyclic groups

Reactive groups capable of ionic bonding

Others
Some of the important reactions involved in reactive compatibilisation

are summarised in Table 1.1 [115].

Introduction

25

Table 1.1: Types of compatibilising reactions used in blending [Ref.115]


Reaction type

Reactive Group

Co-reactive group

Amidation

Carboxylic acid

Amine

Imidation

Anhydride

Amine

Esterification

Carboxylic acid and


anhydride

Hydroxyl

Concerted addition

Maleate and MA

Double bond

Urea formation

Carbodiimide

Carboxylic acid

Urethane formation

Isocyanate

Hydroxyl

Substitution

Amine

Hydroxyl, halide

Ester interchange

Ester

Ester

Transesterification

Ester

Hydroxyl/Phenol

Amide-ester
exchange

Amide

Ester

Aminolysis

Ester

Amine

Amide interchange

Amide

Amide

Acidolysis

Ester

Carboxylic acid

Ring-opening
reaction

Epoxide

Carboxylic acid, MA, hydroxyl,


amine

Ring opening
reaction

Oxazoline

Carboxylicacid, MA, amine,


halide

Remarks

Addition/
Substitution

Addition/
Substitution

Interchange
reaction

Ring-opening
reaction

Lactam

Ionic bonding

Acid

Pyridine, amine, imidazole

Ionic bonding

Ionomer

Ionomer

Ring-opening
reaction

Amine

Ionic bonding

(i)

Amine-anhydride reaction

One of the most frequently used reactions in compatibilisation of


polymer blends is imidation reaction. The reaction is spontaneous and does
not need any molecular catalyst. Schematic representation of the interfacial

Chapter 1

26

chemical reaction with amine end groups of polyamide when maleic


modified polymers are used as compatibilisers is shown in the Fig.1.6.
Maleic anhydride grafted PP [116--117], PE [118], EPR [119], EPDM
[120], SEBS [121], ABS [122], PPE [123] and PSF [124] were used to
compatibilise, a verity of polymer blends, particularly Poly amide to
improve their impact strength, tensile strength, permeability, heat
resistance, crystallization and recycling properties. A major reason for the
wide use of MA functionalised polymers is the relative ease with which
maleic anhydride can be grafted onto many polymers at normal melt
processing temperature with out homopolymerization.

Figure 1.6: Scheme of interface grafting by reaction between anhydride


group and amine end group of polyamide (J. Roeder, R.V.B.
Oliveira, M.C. Goncalves, V. Soldi, A.T.N. Pires, Polym.
Test., 21, 815, 2002.)[Ref.138]

Literature survey also reveals that the imidisation reaction has been
extensively used for the compatibilisation of polymer blends recently [125138].
(ii)

Amine- Carboxylic acid reaction


Amidation results from the reaction of carboxylic acid and amine

groups. Amidation is less efficient and less frequently used when compared
to imidation reaction. Primary amines were found to be more reactive than
other amines towards the carboxylic acid attached to the polymers. This
method has been widely used for several researchers [139-143]. This types
of compatibilisation have been mostly used for improving the impact
strength, tensile strength, permeability, compatibility, morphology and

Introduction

27

recycling properties of PA6, PA66, PA11, etc. An example of interfacial


chemical reaction of SAN-amine with bisphenol -A- polycarbonate to form
SAN-g-PC is given in Fig.1.7. During compatibilisation, interfacial chemical
reaction between amine end group and carboxylic acid group leading to graft
copolymer formation takes place.

Figure 1.7: Reaction of SAN-amine with PC to form SAN-g-PC


(G.Wildes, H. Keskkula, D.R. Paul, Polymer, 40, 5609, 1999)
[Ref. 140].
(iii) Amine-epoxide reaction

Several researchers have employed amine-epoxide reaction as a


route for the compatibilisation of polymer blends [144-151]. The Schematic
representation is given in Fig. 1.8.

Figure 1.8: Scheme of reaction between an amine and an epoxide groups


(R.A. Kudva, H. Keskkula, D.R. Paul, Polymer, 39, 2447,
1998) [Ref. 148]

Chapter 1

28

(iv) Carboxylic acid-epoxide reaction

Researchers have used carboxylic acid-epoxide reaction for the


compatibilisation of immiscible blend systems [152-155]. The Schematic
representation is given in Fig. 1.9.

O
H3C

C O

CH2

O
H3C

CH CH2 + HO C
O

C O CH2

CH CH2

O C

OH

Figure 1.9: Scheme of reaction between a carboxylic and an epoxide


groups (J.K. Kim, S. Kim, C.E. Park, Polymer, 38, 2155,
1997.) [Ref: 152]
(v)

Ring opening reactions

Ring opening reactions include epoxide, oxazoline and lactam rings.


The oxazoline as well as the epoxide rings offer much more flexibility than
any other type of reactions. Epoxide groups can be easily incorporated into
polymers by copolymerisation with functional monomers. Epoxide can
react with hydroxyl, carboxyl and amine groups, while oxazoline is able to
react with carboxylic acid and phenol groups. The lactam ring opening
reaction is less frequently reported in reactive compatibilisation. Poly
(styrene-co-vinyl

oxazoline)

(RPS)

with

copolymerized

oxazoline

functionalised oxazoline groups is the most frequently used reactive


polymer with oxazoline functionalities [156]. Schematic representations of
some ring opening reactions are shown in Fig. 1.10 (a-b). In the last few
years, there has been a rapid increase in the number of literature reports on
the compatibilisation by ring opening reactions [157-159].

Introduction

29
O

R1

R2

H
N

R2

R1

R1

NH2

R2

COOH

R1

N
H

R2
O

Figure 1.10(a): Scheme of reaction between oxazoline with amine and


carboxyl end groups of polyamide (C.Vocke, U. Antilla, J.
Seppala, J. Appl. Polym. Sci., 72, 1443, 1999.) [Ref.157]
R

Epoxy

HOOC PBT OH
PBT
O
a.)

b.) O

PBT OH

OH
R

PBT COOH

OH

Figure 1.10(b): Scheme of reaction between epoxide (a) with COOH (b)
with -OH groups of PBT
(S.C. Jana, N. Patel, D.
Dharaiya, Polymer, 42, 8681, 2001.) [Ref.158]
(vi)

Transreactions

Transreactions take place by the chemical interchange. Random or


block copolymers are formed in these blends by interchange reactions. PC,
PET, PBT and PA have attracted the most attention in terms of
compatibilisation via interchange reactions. Several researchers [160-64]
have made use of this strategy in multiphase polymeric systems. Table 1.2
shows possible interchange reactions during the melting of two polyesters,
two polyamides, and a polyamide and polyester.

Chapter 1

30

Table 1.2: Interchange reactions between polycondensates


(P.S. Archondouli, N.K. Kalfoglou, Polymer, 42, 3489, 2001) [Ref.160]
Alcoholysis

P1-O-CO-P2+OH-P3

Transesterification

P1-O-CO-P2+P3CO-O-P4

Aminolysis

P1-NH-CO-P2 + H2N P3

Transimidation

P1-NH-CO-P2 + P3 CO-NH-P4

Acidolysis

P1-O-CO-P2+ HOOC-P3

Ester-amide

P1-NH-CO-P2 + P3 CO-O-P4

interchange

P2CO-O-P4

(vii)

P1-OH + P3-O-CO-P2
P1-O-CO-P3+P2-CO-O-P4
P1NH2+P3NH-CO-P2
P1-NH-CO-P3 + P2 CO-NHP4
P1-O-CO-P3+ HOOC-P2
P1-NH-CO-P3 +

Ionic interactions

A different approach to compatibilisation of polymer blends is


through ionic bonding instead of covalent bonding. Pyridine, imidazole and
ternary amine groups attached to polymers have been shown to form ionic
bonding with sulfonic acid, carboxylic acid and ionomers and to promote
compatibility of polymer blends [164,165]. Ionic bonding is also formed
between different ionomers [166].
1.6.1.2.3 Factors affecting the reactive compatibilisation

The important factors, which influence the efficiency of reactive


compatibilisations are:
(i)

Reactive group content and end-group configuration

The reactive group content will affect the extent of the interfacial
chemical reaction and the molecular architecture of the in-situ formed
compatibiliser. By increasing the amount of the reactive groups on a
reactive polymer from one to multiple groups, the structure of the graft
changes from a single to a multi-graft comb like structure. At the same
time, the extent of interfacial reaction which is a function of the content of
the reactive groups available will affect the stability of the formed

Introduction

31

copolymer at the interface as well as its physical entanglement with the


compatibilised phases. Paul and co-workers [141,167,168-175] have
performed extensive studies on the influence of reactive group content and
end group configuration of homopolymer and compatibilisers on the
compatibilising efficiency of copolymers.
Loyens and Groeninckx [176] used different compatibilising agents
to obtain a morphology refinement of the PET/EPR blend system and
established that the GMA-induced compatibilisation reaction was much
more effective than the reaction between MA and the PET hydroxyl end
groups. Gonzalez-Montiel et al. [170,175,177] studied the effect of MA
content on the morphology of PA6/PP/PP-g-MA blends and found that the
size and size distribution of PP depended on the content of MA in PP-g-MA
and on the extent of miscibility between PP and PP-g-MA. Oshinski et al.
[168] have reported that the mono functional PA6 was more effective in
dispersing SEBS particles in reactively compatibilised blends of PA6 and
PA66 than PA66.
(ii)

Effect of miscibility of the reactive compatibiliser with one of the


phases

The level of miscibility of the precursor with the phases will


certainly affect the final location of the in-situ formed copolymer during
reactive compatibilisation. A reactive compatibiliser which is fully miscible
with the phase where it is initially incorporated can be expected to provide
the most efficient reduction of the particle size through a decreased
interfacial

tension

and

increased

interfacial

stabilization.

If

the

compatibiliser shows thermodynamic affinity for one of the phases, but is


not miscible with it, an interlayer can be formed at the interface of the
blend phases. The compatibilisation in this situation is not expected to be as
effective in coalescence suppression as for a fully miscible compatibiliser.

Chapter 1

32

At the same time a very low affinity of the compatibiliser for one of the
phases can cause its migration to the other phase.
Majumdar et al. [169] studied the use of imidized acrylic polymer
as a compatibiliser precursor in nylon6/SAN system. One can anticipate at
least three different locations of the block or graft copolymer formed in
blends as illustrated in Fig.1.11. If the imidised acrylic polymer is fully
miscible with the SAN phase, one may expect it to reside primarily within
the SAN phase, with its functional group (A) forming chemical linkages to
nylon6 chains at the interface as shown in Fig.1.11a. This situation is
expected to provide the most efficient reduction in the SAN domains
particle size through a decreased interfacial tension and increased steric
stabilization. Fig.1.11b illustrates the situation in which the functionalized
compatibilisers reside at the SAN interface because it has some
thermodynamic affinity for this phase, but not enough to be miscible with
it. The third situation, shown in Fig.1.11c, arises when the compatibiliser is
even less attracted to the SAN phase and, hence, resides in the polyamide
phase away from the interface. This situation will not result in any
strengthening of the polyamide-SAN interface; however, the formation of
these highly grafted micellar aggregates will increase the viscosity of the
polyamide matrix which in turn, leads to a change in the morphology of the
blend.

Introduction

33

Figure 1.11: Schematic representation of three possible modes of location


of graft copolymers formed by reaction of the imidized acrylic
or compatibilised chains (light lines) with nylon6 dark lines in
PA6/SAN blends (B. Majumdar, H. Keskkula, D.R. Paul,
N.G. Harvey, Polymer, 35, 4263, 1994.)[Ref.169]
(iii)

Stability of the copolymer at the interface

The location of the compatibiliser at the interface between the


individual phases of a blend is an essential and primary requirement for an
efficient compatibilisation and phase morphology stabilisation upon further
re-processing or thermal annealing. A copolymer might be able to locate at
the interface during the first minutes of the compounding process reducing
the size of the dispersed phase and preventing their coalescence. The in-situ
generated copolymer should not leave the interface up on further melt
processing. The pull out of the compatibiliser from the interface depends on
the accumulation of the copolymer chains at the interface, their molecular
architecture and the processing conditions. It is believed that the graft

Chapter 1

34

copolymers are more stable at the interface on account of the more


branched structure.
Groeninckx and coworkers [178-180] reported a series of studies
regarding the interfacial stability of the copolymer. They reported that the
morphology of the uncompatibilised PA6/PMMA blends were highly
unstable

upon

annealing

while

the

reactively

compatibilised

PA6/(PMMA/SMA) blends showed a stable morphology under the same


conditions.
(iv)

Molecular weight of the compatibiliser precursors

Molecular weight of the compatibiliser precursors influences the


blend viscosity, which in turn contributes to the morphology development.
According to Fortelny et al. [181], the decrease in molecular weight and
thus the matrix viscosity decreases the dispersive forces at the origin of
particle break-up and the interface generation which makes the coalescence
favourable. This suggests that the surface area of the interface is partly
controlled by the reactive polymers.
The molecular weight of the reacting polymers also shows a direct
influence on the yield of compatibilisation reaction. At a constant weight
fraction of the reacting polymers, the concentration of the reactive group
attached as an end group of linear chains increases with decreasing
molecular weight. The diffusion of the low molecular weight polymers to
the interface will be faster and this will be contributing to the interfacial
reaction. Thus a decrease in the molecular weight of the reacting polymers
favours the interfacial reaction.

Introduction

35

1.7. Theories of compatibilisation


1.7.1

Hong and Noolandis theory

Hong and Noolandi [182-184] developed a theory for the interfacial


region in three component polymeric systems comprising polymers A and B,
and either a co-solvent or a block copolymer (bcp). The theory was based
on the lattice model which used the mean-field (MF) approximation. It is
formulated using reduced equation of state variables. Finite molecular
weights and conformational entropy effects were considered, but the
excluded volume effects were not (this aspect was later treated by
Broseta et al. [185]. The resulting system of equations can be solved
numerically for the interfacial composition profile, interfacial tension
coefficient, thickness of the interphase, etc. At low values of M w the theory
well predicts F12, but for higher M w the prediction was up to 20% too high.
According to Noolandi [186] and Noolandi and Bunsenges [187], the
effect of copolymer on surface tension between the two phases is mainly
influenced by the contributions from a series of factors such as lowering of
interaction energy between the immiscible homopolymers, the broadening of
the interface between the homopolymers, the entropy reduction in the
system, a decrease in energy of interaction of the two blocks with each other
and a large decrease in the interaction energy of the oriented blocks with
homopolymers. However, it should be noted that the localization of
copolymer at the interface and the separation of blocks into corresponding
homopolymer phases and the simultaneous reduction in interfacial tension
between the phases depend on various factors such as mixing conditions,
interaction of the compatibiliser with the dispersed phase, MW and
composition of the compatibiliser, the rate of absorption and orientation of
the compatibiliser at the interface. Based on these facts and by neglecting the

Chapter 1

36

loss of conformational entropy, Noolandi derived an equation for the


interfacial tension reduction as:

'J

d ) c 1 2 F  1 Z c  1 Z c exp Z c F 2

.(1.5)

where d is the width at half height of the copolymer profile reduced by the
Kuhn statistical segment length, ) c the bulk copolymer volume fraction of
the copolymer in the system, Z c the degree of polymerisation of the
copolymer and F the Flory-Huggins interaction parameter between A and B
segments.
1.7.2 Leiblers theory

Leibler [188] examined the emulsifying effect of an A-B copolymer


in immiscible blend of polymers A and B and predicted a reduction of
interfacial tension caused by equilibrium adsorption of the copolymer at the
interface. He suggested that at equilibrium, the droplets size distribution is
controlled by rigidity and spontaneous curvature of radius of the interphase,
both dependent on the copolymers molecular constitution. The theory
predicted reduction of the interfacial tension coefficient, 'J , caused by
equilibrium adsorption of a copolymer at the interface. For well-chosen
compositions and MWs of the copolymer, low values of 'J are to be
expected. This suggests a possible existence of thermodynamically
controlled stable droplet phase, in which the minor phase homopolymer
drops are protected by an interfacial film of the copolymer, interfacing the
matrix polymer.
For long copolymer chains (the wet brush case i.e., copolymer
overlap strongly and stretch but still homopolymers can penetrate the
brushes), the reduction of the interfacial tension coefficient should follow the
relation [189]:

Introduction

'J

37

 kT a 2 3 4

13

2 5 3

6 a Z

CA

Z A 2 3  Z CB Z B 2 3

(1.6)

where Z CA and Z CB are the number of A and B units in the copolymer,


respectively, Z A and Z B the degree of polymerisation of A and B,
respectively, a the monomers unit length and 6 the interfacial area per
copolymer.
In the case of dry brush limit (when copolymers are expected to be
stretched but homopolymers should not penetrate the copolymer layer
appreciably, the interfacial tension reduction 'J obtained by the brush
limit which is independent of the homopolymer MWs.
'J

J0

48 P 3 2 F N 1 2

(1.7)

where J 0 is the interfacial tension of polymer blend without a compatibiliser


and P is the chemical potential which is given by the equation:

ln I   f F N

(1.8)

where f is the volume fraction of the component in copolymer which is


miscible to homopolymer forming the dispersed phase and
I

I0
Im  Id exp ^F N A  N B `

(1.9)

where I0 , Im and Id represent the volume fraction of the copolymer, matrix


and dispersed phase, respectively, N A and N B are the number of segments
of the component in the copolymer miscible to the homopolymer forming the
dispersed phase and that miscible to homopolymer forming the matrix phase,
respectively.

Chapter 1

38

The surface coverage of one copolymer, i.e., the surface area


occupied by one compatibiliser molecule per unit volume at the interface, is
related to P and F as
6 2
b

3 2

1 2

N P

(1.10)

where b is the Kuhn length.


1.7.3 Vilgis and Noolandis theory

Vilgris and Noolandi [190] computed interfacial tension ( J )


interfacial thickness ('l) and the concentration profiles in a system
comprising polymer A, polymer B and an arbitrary bcp X-Y. It was found
that addition of X-Y to A/B blends could reduce J . The reduction increases
with MW of the copolymer. Computations were carried out for different
values of Fij and Zc. Strong localization effects of X-Y were observed when
the interactions between the blocks and the homopolymers were increased.
Thus, the competitive interactions of the blocks with homopolymers were
shown to promote interfacial activity. The reduction of J in A/B blend upon
addition of copolymer X-Y was expressed as:

'J

 1 Z c exp Z c F1 2  F 2

for : F1 { F BY

F AX

F XY

F AB and F 2 { F AY

.(1.11)

F BX ! F1

The work suggested possibilities of designing a universal compatibiliser


operating on the principle of competitive interactions between polymers and
the copolymer's blocks.
1.7.4 Anastasiadis theory

A generalized gradient theory of the interface was developed by


Anastasiadis [191]. The approach is based on the assumption that the

Introduction

39

composition gradient is small compared to the reciprocity of the intermolecular


distances. Under these circumstances the free energy density, g, can be
written as a power series, truncated after the square term. In essence, the
theory determines the difference in the density fluctuation per unit interfacial
area between polymer mixture and a system in which the properties are
homogenous. The theory predicts that,

Q 12

IE

N'g I 1 2 dI

2
N {  w 2 g wI w 2I  w 2 g w I

.(1.12)
(1.13)

1.7.5 Utracki and Shis theory

Utracki and Shi [192] derived a semi-empirical relation between the


interfacial tension coefficient ( J 12 ) and compatibiliser concentration by
assuming an analogy between addition of bcp to a polymer blend and
titration of an emulsion with surfactant. According to the authors:

J 12

^ IJ

CMC

 ImeanJ 0 I  Imean `

where J CMC { J 12 Ic

.(1.14)

ICMC , Imean ICMC  I0 2

1.7.6 Tang and Huangs theory

Based on the fact that upon the addition of compatibiliser, interfacial


tension J decreases and on assumption that the decrease is directly
proportional to the interfacial tension difference at a particular compatibiliser
concentration C and CMC, then:
dJ


dC

K J  J s

..(1.15)

where K is the rate constant for the change in interfacial tension with
concentration of the compatibiliser, J the interfacial tension at a given

Chapter 1

40

compatibiliser concentration, C and J s the interfacial tension at CMC. From


the above expression, Tang and Huang [193] eventually derived the
following equation:

R  Rs

(R 0  R s )e  kC

...(1.16)

where R0, R and Rs are the average radius of dispersed particles without
compatibiliser, at a given compatibiliser concentration and compatibiliser
concentration at CMC respectively. A plot of ln R  Rs versus C can be
used to obtain k from the slope.
1.7.7 Paul and Newmans theory

According to Paul and Newman [194] the interfacial area per unit
volume occupied by each compatibiliser molecule is given by the expression:
6

3I M

RNW

..(1.17)

where N is Avogadro number, M the number average MW of the


compatibiliser, R the average radius of the dispersed phase, I the volume
fraction of the dispersed phase and W the weight of the compatibiliser
required per unit volume of the blend. When I and M are kept constant,
6 depends on the values of R and W. R decreases with increase in the
weight fraction of the compatibiliser and 6 may either decrease or not
change or increase.
1.7.8 Favis theory

Favis and co-workers [195,196] have used the geometrical


considerations about the macromolecular size in order to make a critical
analysis of the minimum amount of bcp needed to saturate the interface in
the melt mixing of immiscible polymer blends. For the case of dispersed
spherical domains, an expression has been developed which contains only

Introduction

41

molecular parameters such as the number of bonds, the characteristic ratio


and the composition of the bcp used to compatibilise the blend. According to
the authors, the critical saturation concentration ( Ccr ) value of the bcp is
given as:
Ccr

S R2 M A 3 1
k
NRg2 4S R3 UWA

3kM A
4 Rg2 RN UWA

..(1.18)

where M A is the MW of block A, Rg is the radius of gyration of A block, N is


the Avogadro number, U is the density of the bcp, k is the number of block
per cubic element, WA is the weight fraction of A phase in the copolymer and
R is the radius of the dispersed phase.
1.8

Dynamic Vulcanization

Dynamic vulcanization is the process of crosslinking rubber in-situ


using curing agents during its melt mixing with molten plastic. The product
thus produced by simultaneous mixing and crosslinking of a rubber with a
thermoplastic is known as Thermoplastic vulcanizates (TPVs) or Dynamic
vulcanizates (DVs). It is a route to new thermoplastic elastomers (TPEs),
which have many properties, as good as, or even in some cases better than
those of elastomeric block copolymers. TPVs comprise the fastest growing
thermoplastic elastomer market with an annual growth rate of 10-12%.
Dynamic vulcanization was first claimed by Gessler [197] in 1962
and then developed by Fisher [198] in 1972, and Coran et al. [199,200] in
1978. When EPDM is crosslinked during its blending with nylon, the
blends become a special type of thermoplastic elastomer known as
thermoplastic vulcanizates (TPVs) [199]. The double bonds in EPDM act
as curing sites for cross-linking with peroxides, sulphur, radiation or other
curatives.

Chapter 1

42

Coran and Patel carried out extensive studies on dynamically


vulcanized TPEs in the 1980s [201-207]. During the past several years,
many studies have been reported on the structure and properties of various
TPV blends obtained by dynamic vulcanization [208-222]. The purpose of
the dynamic vulcanization of elastomeric thermoplastic rubber blends is to
provide compositions that have improved mechanical properties, grater
resistance to attack hot oils, greater stability of phase morphology in the
melt, and more reliable thermoplastic fabricability.
Upon the addition of the crosslinking agent, the viscosity of the
rubber phase increases and at a sufficient degree of curing phase inversion
occurs [223]. This transformation is shown in the Fig.1.12.

Figure 1.12: Morphology of a thermoplastic/rubber blend before and after


dynamic vulcanization

The high degree of crosslinking of the rubber phase inhibits the


process of strand break, reduction of interfacial area, and also the
coalescence of the dispersed particles. As a result, the dispersion in a
thermoplastic /rubber dynamic vulcanizate is very irregular as shown in the
figure. The thin thermoplastic layers between the crosslinked rubber
particles are some how elastic and act as a kind of glue between the
crosslinked rubber domains [224].

Introduction

43

Dynamic vulcanization is not entirely satisfactory for making soft


compositions, because as the rubber level increases, the resulting
compositions become more difficult to produce. Abdou-sabet [225] found
that in a process for preparing TPVs based on PP/EPDM blend by dynamic
vulcanization, improved properties could be achieved when the mixing
shear rate was at least 2000 S-1

in a twin-screw extruder, with the

thermoplastic component in the molten condition at about 170-230C.


Many of the TPVs found commercial applications, especially in the
automotive sector. The first commercial application was based on the
patents by Fisher [226-228] where the dynamic partial vulcanization of
EPDM in a PP matrix was accomplished by limiting the amount of
peroxide. Naskar and co workers [229] demonstrated that the use of
dicumyl peroxide in combination with triallyl cyanurate as crosslinking
agents provides a good overall balance of physical properties of PP/EPDM
TPVs. Kumar et al. [230] have reported on the morphology and mechanical
properties of dynamically vulcanized nylon6/66 and acrylonitrile butadiene
rubber TPEs. Thermoplastic elastomers based on recycled high-density
polyethylene, ethylene-propylene diene monomer rubber was studied by
Karger-Kocsis et al. [231]. Nakason et al. [232] reported on the
achievement of excellent mechanical properties in dynamically crosslinked
maleated NR/PP blend that contains a higher proportion of elastomer. The
authors reported on the use of MA modified NR enabled a finer dispersion
of NR phase in PP in blend composition. Huang, [233] have reported on the
effect of curatives and compatibiliser in the nylon/EPDM blend system.
Groeninckx and coworkers [234-236] developed a new method to
prepare TPV based on PA6/EPDM blends with high amount of rubber
using compatibilisation and dynamic vulcanization. The AFM picture of

Chapter 1

44

non-strained PA6/ EPDM-g-MA TPVs with 50wt % rubber is given in the


Fig.1.13. A fine dispersion of the EPDM phase in the nylon matrix can be
seen in the figure due to the reactive compatibilisation and crosslinking.

Figure 1.13:

1.9

AFM phase image of a PA6/EPDM g-MA TPV with 50wt%


rubber (J.Oderkerk, G.De Schaetzen, B.Goderis, L.Hellemans,
G.Groeninckx, Macromolecules, 35, 6623, 2002.) [Ref.236]

Morphology of Polymer blends

The term morphology refers to the arrangement of polymer


molecules into amorphous or crystalline regions and the manner in which
they are organized into more complex units. The morphology of a multicomponent polymer system (polymer blend) indicates the size, shape or
spatial distribution of the component phases with respect to each other and
is referred as phase morphology. Since it is well established that most of
the properties such as mechanical, optical, rheological, dielectrical and
barrier properties of polymer blends are strongly influenced by the type and
fineness of phase structure. The study of the control of the morphology of
polymer blends has emerged as an area of continuous interest to polymer
material scientists for the last few decades [237-241].

Introduction

45

When two immiscible polymers are mixed, the size, shape and
relative distribution of one phase into the other depend on material
parameters such as blend composition, viscosity ratio, elasticity ratio and
interfacial tension as well as processing conditions like temperature, time,
intensity and type of mixing and nature of flow. Therefore the greatest
challenge in the field of multiphase polymer blend research is the
restructuring of polymers via judicious control of the melt flow during
processing and the interfacial interactions. The mechanism of development
of morphology from pellet sized or powder sized particles in polymer
blends are directly derived from the complex interplay of material
parameters and processing conditions. As a result of this, for a given blend,
different types of morphologies are possible. However, from the point of
view of the performance, they can be categorized into four basic
morphology types (Fig.1.14).
x

Matrix-dispersed particle structures

Matrix-fibre structures

Lamellar structures

Co-continuous structures
Other important types of morphologies are fibrillar, core shell,

onion ring like, etc. A schematic representation of different types of


morphologies of polymer blends is presented in Fig. 1.14 to Fig.1.7. It is
important to mention that, the final properties of polymer blends are
dependent on the finial morphology of the blend.

46

Chapter 1

Figure 1.14: Types of morphology in immiscible polymer blends,


illustrated by SEM photographs of cryofractures (a) Dispersed
structure (b) Matrix-fiber structure(c) Lamellar structure
(d) Co-continuous structure(D.R Paul and Petra Potschke,
J.Macro. Sci. 43,87,2003)

Figure 1.15: SEM micrograph of a fibrillar morphology (Reproduced


from C.W Macosko, Macromol.Symp.149, 171,
2000.)[Ref.238]

Introduction

47

Figure 1.16: SEM micrograph of a core shell morphology (Reproduced


from H.F Mark, M.Bikales, C.G Menges, J.I Kroschwitz,
Encylopedia of Polymer Science and Engineering. 2nd Ed.,
John Wiley & Sons Inc., New York,1987)

Figure 1.17: Transmission electron microscopy (TEM) microscope of an


onion ring morphology (Reproduced from H.F Mark,
M.Bikales, C.G Menges, J.I Kroschwitz, Encylopedia of
Polymer Science and Engineering. 2nd Ed., John Wiley &
Sons Inc., New York, 1987)
1.9.1 Mechanism of morphology formation

The formation of morphology in polymer blends, in which one


phase forms the dispersed phase can be described under microrheological
aspects by the following ratios and numbers [242-245]
Viscosity ratio of the components

OK

K d T , J
K c T , J

.(1.19)

Chapter 1

48

where d is the viscosity of the dispersed phase and c is the viscosity of the
matrix phase.
Elasticity ratio of the components

OT

T d T , J
T c T , J

.(1.20)

where d is the coefficient of elasticity of the dispersed phase and c is the


coefficient of elasticity of the matrix phase.
Stress ratio (Capillary number or Weber number)

We

K.J .R
J dc

.(1.21)

where dc is the interfacial tension and R is the particle radius.


Relative duration of the deformation processes as a ratio of
deformation and capillary number k

J .t v

K.J .R / J dc

t v .J dc
K .R

.(1.22)

where tv is the residence time


Coalescence (probability of particle collision Pcoll)
Pcoll

6.J .M d2
S 2 .R 3

.(1.23)

Grace [246] investigated droplet breakup in shear and elongational


flow and found that droplet destruction in a simple shear field takes place
most easily if the viscosity ratio is approximately 1. The deformation
conditions of fluid droplets of an emulsion in a shear-field have been
classified by Rumscheid and Mason [247] (Fig1.18)

Introduction

49

Figure 1.18: States of droplet deformation of Newtonian media in shear


fields (Rumscheid and Mason, J.Colloid Sci.16, 238, 1961.)
1.9.2

Morphology development
There has been a flurry of activity in the area of polymer blend

morphology development over the last few years. Fig.1.19 shows the
important mechanisms during blending of immiscible polymers.

Figure 1.19: Important mechanisms in morphology development during


polymer blending of nylon/EPM rubber blends (C.E Scott,
Ph.D thesis, University of Minnesota, 1990.)

Chapter 1

50

Melt blending is normally applied in the case of solid pellets or


powders in the millimeter size range. These are sheared inside using an
intensive mixing device such as an extruder or batch mixer. These
millimeter size domains melt and break up into micrometer or nano meter
sized domains during the initial softening stages.
Scott and Macosko [248,249] showed that sheeting occurred during
initial melting stages in twin-screw batch mixers, Sundararaj et al. [250]
reported sheet formation in miniature cup and rotor mixers, and Sundararaj et
al. [251,252] also showed pellets stretching into sheets in simple shear flow. It
was thought that sheets form when pellets melt on the hot barrel [249], but
later studies showed that sheets formed in the molten state [251-259].
1.9.2.1 Initial morphology
It was found that the dispersed phase breaks up by stretching into
sheets [249,260,261] and these sheets subsequently broke up into smaller
domains. Fig.1.20 is a summery of work by Macosko and coworkers who
showed how a pellet deforms into a sheet and subsequently breaks up into
droplets [249, 253, 260,262,263,264].

Figure1.20: Schematic representation showing morphology development


mechanisms during polymer blending process (C.W.Macosko,
P.Guegan, A.K.Khandpur, A.Nakayama, P.Marechal, T.Inoue,
Macromolecules, 29, 5590, 1996) [Ref.264].

Introduction

51

The figure also shows the effect of stabilization on final drop size.
Once domains reach the micron size scale, they may be stretched into
filaments and are then broken into droplets. At this size scale, interfacial
forces become important and pull in the edges of the stretched domains,
giving cylindrical or filament type morphology. The stretching and
breaking up of filaments is due to the combined effect of high shear zones
and low shear zones in the mixture [265]. The domains are stretched in the
high shear zones and then relax and break up in the low shear zones via
Rayleigh type instabilities. It may be possible to form drops directly from
sheets but only at very low shear rates. Much polymer blending work
reports filaments even at the end of the mixing process [266,260], and this
may be a result of a high shear zone at the end of the process [265]. Break
up phenomena in polymer blends are non-Newtonian in nature
[243,249,260,261,267-270].
Fig.1.21 shows an example of an investigation of the dispersion
behaviour of real polymer blends. Favis and Chalifoux [271] investigated
blends of polypropylene (PP) and polycarbonate (PC) with respect to the
correlation between the average droplet size and the viscosity ratio. The
viscosity ratio is found to have a marked effect on the morphology of the
dispersed phase.

52

Chapter 1

Figure 1.21: Average droplet diameter as a function of viscosity ratios of


PP/PC blends (B.D. Favis and J.P. Chalifoux, Polym. Eng.
Sci. 27,1591,1987.) [Ref.293]
The mechanism of destruction of strongly elongated dispersed
structure was described theoretically by Taylor and Tomotika, and was
experimentally demonstrated by Elmendrop as shown in Fig.1.22 in PA/PE
blends.

Figure 1.22: Schematic wave formation in deformed fibres and their


breaking off into droplets (Top), Droplet formation in an
experiment that consists of PA6 fibres in a PE matrix at
200C (Bottom). (J.J. Elmendorp and A.K. Van der Vegt,
Polym. Eng. Sci.26, 1332,1986.)[Ref.295]

Introduction

53

In this example the polymer blend system have >1. If a


polystyrene (PS) droplet of nearly the same viscosity as PE is deformed
under shear above a critical shear rate, it can fall apart into two particles.
The bigger the droplet and the lower the interfacial tension, the lower is the
shear stress needed for droplet break up (Fig.1.23a and 1.23b). In the PP/PS
blend, it is impossible to obtain a fine dispersion of PS, as the PS has a
higher viscosity than the PP matrix (Fig.1.23c). The high interfacial tension
of the dispersed phase results in the formation of ball shaped PS particles.
Because of the high viscosity of the PS, coalescence cannot progress too
far. Furthermore, it can be seen that because of the strong immiscibility of
the components, no interface is formed. So the PS particles lay detached in
the matrix.

Figure 1.23: Examples of melt droplets under low deformation. PS droplets


in a PE matrix under shear at 200C (a) Below a critical shear
rate, (b) Just above the critical shear rate (c) SEM micrograph
of the phase morphology of a PS/PP blend. (Radusch in
Frontiers in the Science and Technology of Polymer
Recycling, 191, 1988.)
Li and coworkers [272] have shown that the presence of a
compatibiliser increases the rate of melting by reducing the interfacial

Chapter 1

54

thermal resistance and thus increasing the blends overall thermal


conductivity. The presence of the compatibiliser at the interface may also
decrease the amount of interfacial slip, and thus, at equivalent shearing
conditions, leads to greater deformation of the dispersed phase.
Bourrry and Favis [273] indicated that the morphology development
did not depend on melting but on the flow fields seen by the blend. It has
been seen that the sheeting mechanism occurs in the melt state well above
the

polymer

melting

temperature

[250-257],

indicating

that

the

phenomenon is more dependent on polymer rheological properties than the


actual melting region. Modeling of this sheet formation and the break up
has been done [251,255,256,274,275] and shows that the rapid decrease in
morphology can be explain by deformation into sheets but not by
deformation into filaments [275].
1.9.2.2 Co-continuous phases and phase inversion
Phase inversion is defined as a phenomenon whereby macroscopic
conditions like mixing composition, viscosity and surface tension change a
continuous phase into a discontinuous phase. The phase inversion often
happens in a zone containing a cocontinuous phase morphology.
When polymer blends are prepared from a mixture of solid pellets
or powder the melting order of the components is important in determining
the morphology development [254,255,258,267,276-281]. If the minor
component, soften first, then it will initially form the matrix surrounding
the pellets of the major component. As higher temperature is reached
during processing, the major component reaches sufficient concentration in
the melt to envelope the minor component and the major component
becomes the matrix. The mechanism of the processing phase inversion

Introduction

55

shown schematically in Fig.1.24. Lazo and Scott [254] showed a similar


mechanism.

Figure 1.24: Phase inversion mechanism (a) sheets are pulled off the
softening pellets near the softening transition of the major
phase. (b) The sheets from lamellar domains inside the
minor phase(c) break up into irregular pieces (the minor
phase is also breaking up at this point) until (d) phase
inversion occurs during processing through coalescence of
the major phase domains. (U. Sundararaj, C.W. Macosko,
C.K. Shih, Polym. Eng. Sci. 36, 1769, 1996) [Ref: 262]
Various authors found that phase inversion was dependent on the
ratio of the blend composition and the ratio of the viscosities [282,283]:

M1 K 2
.
M 2 K1

(1.24)

resulting in the following morphology variants:

X >1: Phase 1 is continuous and phase 2 is dispersed


X <1: Phase 2 is continuous and phase 1 is dispersed.
X | 1 : Cocontinuous phase morphology or phase inversion occurs

Chapter 1

56

The above equation implies that only the viscosity ratio of the
components determines the volume fraction at which phase inversion takes
place.
Fig. 1.25 shows schematically the progress of the zone of continuity
in a theoretical polymer system.

Figure 1.25: Phase inversion in binary polymer blends. The theoretical


scheme is based on the Krieger-Dougherty equation (J.M.H.
Janssen, Dynamics of liquid-liquid mixing, Wiley, New
York, 115,1997.) [Ref.285]
Theoretically, cocontinuous phase can be found even for strong
concentration differences if certain viscosity ratios are provided. The curve
in Fig.1.28 is obtained by the application of modified Krieger Dougherty
equation [284], which was developed for the determination of the viscosity
of compounds containing polymer droplets in a polymer matrix [285].
Shih and coworkers [262,267,277,280] used visualization and
mixture torque rheology and showed that a blend goes through four distinct
rheologic regimes during processing. In some case, during phase inversion,
an order of magnitude increase in torque is seen [262,267, 277,280], and in
other case an initial sharp decrease in torque followed by a sharp increase
in torque is seen [279-281]. Phase inversion is usually associated with a

Introduction

57

thermodynamic change where the dispersed phase inversed to become the


major phase to minimize the free energy.
Shih [277] postulated that initially the minor component forms the
matrix with closely packed the pellets of the major component. As the
major component begins to be dispersed in the minor component matrix a
packing arrangement or percolation threshold was reached, and the blend
inverts in phase continuity. Sundararaj and Coworkers [262] investigated
the phenomenon in more detail by mixing reactive and non-reactive blends
in a batch mixer and studying dispersed phase morphology by selectively
extracting the matrixes and viewing the products under SEM. This would
correspond to extracting the minor phase during the initial stages of
blending to view the dispersed major phase.
It was found that the major phase pellets are initially deformed into
sheets, and when a critical composition of major phase domains is reached,
the mixture undergoes phase inversion. Scott and Joung [286] studied the
effect of viscosity ratio (r = minor / major) on phase inversion, particularly
at early mixing times. They reported that r >0.1, the time to phase
inversion was relatively constant; however when r <0.1, the time to
inversion increased as the viscosity ratio decreased. Lazo and Scott
[254,255] showed that phase inversion can occur even in simple shear
flows and that melting is not required for the phase inversion phenomenon.
They also indicated that, besides rheology and component concentration,
the thickness of the minor component domains should also be considered
since the minor component sheets need to break up before phase inversion.
1.9.2.3 Final morphology
It is important to mention that, the final properties are dependent on
the finial morphology and this is a balance between deformation and

Chapter 1

58

disintegration phenomena on one hand and coalescence on the other. For


this reason a variety of morphological structures are obtained by varying
the composition. Based on the nature of application, different types of
morphology are sought. For example, for barrier properties, a lamellar
structure is required, where as for impact properties, a droplet-in-matrix
morphology is preferred.
1.9.2.3.1 Breakup and coalescence balance
The size and shape of the dispersed phase depends on several
material and processing parameters, including rheology, interfacial
properties and blend composition. A review of early work in drop break up
and coalescence in polymer blends was given by Utracki and shi [287].
Tokita [288] suggested that an equilibrium drop diameter occurs from
continuous break up and coalescence of the dispersed phase. Drop break up
has been studied extensively by various researchers [289-298]. Coalescence
of dispersed particles results from hydrodynamic and surface effects and is
directly opposed to the mixing of the components. Coalescence depends on
the concentration of the dispersed phase, the average particle size and the
molecular mobility of the interface between the matrix and dispersed phase.
Thus an increase in matrix viscosity will result in a higher dispersion of the
melt droplets, simultaneously the viscosity increase will hinder droplet
coalescence. Coalescence during polymer blending has been studied more
recently [299-309]. Coalescence of drop is shown schematically in
Fig: 1.26. Fortelny and coworkers [310-312] found that the amount of
coalesence in blends depends on matrix phase viscosity and dispersed
phase volume fraction.

Introduction

59

Figure 1.26: Idealised depiction of coalescence in polymer blends. Drops


are brought close to each other by the shear field and then
the matrix film between the drops thins.
1.9.2.3.2 Effect of copolymer on coalescence
The particle size decreases when premade copolymers [313-319] or
reactive polymers [313,320-322] are used. Similar to Newtonian emulsions, an
emulcification curve concept (Fig.1.27) has been advanced for polymer
blends using premade copolymers [317-319] or reactive polymers [320].

Figure 1.27: Emulsification curve for polystyrene/ethylene-propylene


rubber 90:10 blend compatibilised with SEBS triblock
copolymer.

Chapter 1

60

The particle size is seen to decrease when low concentrations of


copolymer compatibiliser is added to a blend, and a critical compatibiliser
concentration exists above which there is no change in particle size. This
suggests that there is a point where the copolymer saturates the interface
and the addition of any more compatibiliser will have no effect. In the case
of block copolymers, this extra amount can exist in the form of micelles.
When

the

dispersed

phase

concentration

is

increased

in

uncompatibilised blends, the particle size increases, but for blends


containing compatibiliser, the particle size remains fairly constant. This
observation suggests that coalescence is suppressed by the addition of
copolymers. Some researchers have reported that a lowered interfacial
tension was responsible for morphology stabilisation [317]. Most of the
research works indicate that the stable morphology is due to the
suppression of coalescence.
There are two major theories proposed to describe the suppression
of coalescence. Sundararaj and Macosko [313] described a steric
interaction between droplets due to the copolymer at the interface, shown in
Fig.1.28a. Milner and Xi [323] suggested that a local concentration gradient
was created when two drops come together leading to a Marangoni stress
that slowed the rate of film drainage between the drops, thereby
suppressing coalescence (Fig. 1.28b).

Introduction

61

Figure 1.28: Mechanism for suppression of coalescence in compatibilised


blends. The copolymer may reduce coalescence effects by
(a) steric repulsion of interacting drops or (b) creating a
surface tension gradient (Marangoni forces)(S.P. Lyu, F.S.
Bates, C.W. Macosko, Macromolecules, 35,7855,2002.)
[Ref. 304]
Lyu et al. [304] showed that the minimum coverage required for
coalescence suppression in PS/HDPE 87:13 blends with polystyrene
/Polyethylene (PS/PE) block copolymer did not depend on shear rate but
did depend on copolymer molecular weight. Both of these observations
support the steric interaction mechanism but are in disagreement with the
Marangoni force mechanism. However, Ha et al. [308] performed model
experiments for coalescence of two polybutadiene drops in a poly
(dimethylsiloxane) (PDMS) matrix, and they concluded that the most
probable mechanism was Marangoni forces. However, the results were not
definitive since they found the coalescence was insensitive for the
copolymer concentration for high viscosity ratio systems, which is not
consistent with the Marangoni force mechanism but is consistent with the
steric interaction mechanism. It is accepted that some type of stabilisation

Chapter 1

62

is required to create immiscible polymer blends with tailored morphology


and properties.
1.9.2.4 Effect of processing and material parameters on morphology
Many researchers have tried to change the blend morphology using
processing parameters such as shear rate, temperature, mixing time, mixer
type and composition. Among these the most important parameter is blend
composition. The final domain is about 1m for the majority of
uncompatibilised blends, regardless of processing conditions. However,
subtle changes in particle size can have important consequences for
mechanical properties, and therefore there were many studies about the
effect of processing parameters on morphology.
The viscosity ratio and other material rheological parameters have
been shown to be important in determining break up. Wu [292] and Favis
and Chalifoux [293] performed the first investigation in this area. Both
correlated the domain size with the viscosity ratio (r = d /m). But the
relationship was not exactly same as the reported in the Newtonian
literature.
Interfacial tension is another key parameter. Most polymer blends
have an interfacial tension in the range 0.002 to 0.005 N/m, which is much
lower than that of conventional fluid systems like oil/water. During drop
deformation, viscous forces balance the interfacial forces, and the capillary
number is the ratio of these forces as shown below.
Ca

K mJ R
*

..(1.25)

where m is the matrix viscosity, is the shear rate, R is the drop radius and
is the interfacial tension. When the viscous forces are much greater than
the interfacial forces, drop break up is expected. The capillary number is

Introduction

63

more appropriate for polymer blends since, due to the high polymer
viscosity, the flows are typically laminar flows, and viscous forces
dominate. Wu defined a critical capillary number (Weber number) for
viscosity ratio above which drop breaks up occurred.
2C a

4K r

r0.84

(1.26)

The Weber number is widely used in emulsions since inertial forces are
important. Favis and Chalifoux [293] showed similar trends in their work.
1.9.2.4.1 Effect of composition
Much of the early research on polymer blends concentrated on the
effect on the composition since by changing the composition, one could
easily alter final blend properties. It was found that increasing the
composition typically increased particle size up to the cocontinuous
morphology region [299,293,313,322,324]. There have been few
exceptions to this general observation at higher concentrations [325]
because of the influence of the dispersed phase viscosity on dispersed phase
domain deformation. Sundararaj and Macosko [313] showed that the
particle size increased with concentration of dispersed phase due to
coalescence in uncompatibilised blends. At low concentrations, the particle
reached a limiting size. The limiting size should correspond to the dilute
solution limit. It was found that the drop size was greater than that
predicted by Taylors limit [326,327], but lower than that predicted by
Wus correlations. The lower drop size observed at low concentration is
lower than that obtained by Wu because coalescence was present in Wus
data. The discrepancy with the Taylor limit was explained to polymer
elasticity for the drop.

Chapter 1

64

For 1 wt % blends, Evaraert et al. [328] found a correlation similar


to Wu but with different fitting coefficients:
2C a

1.2K r

r0.45

(1.27)

In addition, they found that at low viscosity ratios Taylors limit is valid,
but at higher viscosity ratios, the drop size is greater than Taylors limit and
lower than Wus correlation. Taylor predicts no break up for viscosity
ratios above 4, and yet break up is seen in many polymer blends with much
higher viscosity ratios [292,293,313,328]. Recent work using model
mixtures has shown that polymer drops can break up in simple shear at
viscosity ratios above 4 [251,254,256,257,259,329,330,]. It is now clear
that polymer drops behave very differently from Newtonian drops and that
Ca or r alone may not be sufficient to describe the break up.
1.9.2.4.2 Effect of shear rate
The customary expectation is that the dispersed phase domain size will
decrease with increased shear rate. Even when considering the shear thinning
nature of polymer viscosity, the shear stress continues to increase with
increasing shear rate so drop size should decrease at higher shear rate.
However, most works studying the effect of the shear rate on morphology in
polymer blends do not show this trend. As the shear rate was increased Favis
[268] found a modest decrease initially and then a levelling off in the particle
size. White and coworkers found that changing the shear stress did affect the
particle size [331] while Walczak found that changing the shear stress by a
factor of three had little effect on structure [332]. During mixing, Plochocki et
al. [291] observed that the drop size decreased initially as the shear rate was
increased, and then the drop size actually increases at higher shear rates. The
authors explained that an optimum energy input or specific energy
consumption (SEC) gave a minimum drop size. Ghodgaokar and Sundararaj

Introduction

65

[270] also observed a minimum drop size at an intermediate shear rate and use
a force balance to predict this behaviour.
1.9.2.4.3

Effect of mixing time

As previously mentioned, dispersed phase domain size decreases


very rapidly in the initial mixing stages. After one minute in the batch
mixer, there is very little change in the morphology [249,260,333-337].
Mixing for up to 10 minutes in the batch mixer show very little change
from the morphology seen at 1min [249,289,290]. Mixing for longer times
actually leads to coarsening, and particle size increase between 10 and 20
minutes of mixing [322]. The starting particle size for polymer mixing is
usually dictated by feeding limitations-the particle size must be small
enough to be fed into the mixer but not too small or powdery that it is
difficult to handle. Therefore, a millimeter size feed is normally used.
1.9.2.4.4

Effect of temperature

Temperature can have varying effects on the polymer morphology.


Thomas and Groeninckx [322] reported an increase in particle size with
temperature for nylon/EP (ethylene Propylene) rubber blend but indicated
that, this may be due to a decrease in the matrix phase nylon viscosity at
higher temperatures. In addition, at higher concentrations, the lower matrix
viscosity may enhance coalescence. Temperature has a marked effect on
component polymer properties so it is difficult to make any sweeping
generalisation about the effect of temperature on morphology. However,
temperature definitely influences the morphology, and it must be
considered when developing new blends.
1.9.2.4.5 Effect of mixture type
Majority of the work in polymer blending has been performed on batch
mixers or twin- screw extruders. Single screw extruders do not have as much

Chapter 1

66

capability for mixing and do not have the folding reorientation. A mechanism
that has been found to be important for blending [265,338,339]. For batch
mixers and twin-screw extruders, morphology development mechanisms are
similar and the final morphology at matched conditions is also similar
[260,322]. It is also important to note that researchers using batch mixers [293]
and those using twin screw extruders [292] achieved similar morphologies,
mechanisms and conclusions about the polymer blending process. However,
many laboratories, especially those at Universities, have used miniature
mixtures to simulate larger scale mixers. One of the most popular miniature
mixers is the Minimax mixer [340].
1.9.2.4.6 Model experiments
Because of the difficulty in following a particle in the complex flow
paths of a twin-screw extruder or twin-rotor batch mixer, several
researchers have used model flow fields to study polymer blending [251253,256,263,307-309,341,342]. Fig. 1.29 shows that polymer pellet break
up via sheeting is seen even in simple shear flows and it was confirmed that
this type of deformation occurs in the melt state [251,253,256].

Figure 1.29: Sheeting mechanism in the melt state. A sheet formed when
a polypropylene pellet in a polystyrene matrix is subjected to
a shear flow in parallel plates
Using this model experiments, researchers were able to investigate
the critical parameters responsible for break up and have developed rules to

Introduction

67

determine when particular break up mechanisms will dominate


[257,251,253,343,344]. A summary of four different breaks up mechanisms
seen in simple shear flow is shown in Fig.1.30.

Figure 1.30: Four different polymer drop break up mechanisms seen in


simple shear flow. (a) The drop may form a sheet in the flow
direction and break up, (b) The drop may erode at the surface
slowly, (c) The drop is stretch in the vorticity direction and
break up, or (d) the drop may spit out small droplets via a tip
streaming mechanism. A combination of this break up
mechanisms can occur for the same blend depending on the
temperature, shearing conditions, and drop size.
1.9.3 Morphology of dynamic vulcanizates
Many papers appeared in the literature describing the phase
morphology formation of non-reactive polymer systems consisting of a
thermoplastic and a rubber component [283]. Several authors have also
studied morphology formation in reactive polymer systems, especially
thermoplastic rubber blends systems with cross-linked rubber phases [313,
345353]. In the case of selective cross-linking of a rubber phase during
dynamic vulcanisation of thermoplastic rubber blends, only one component
changes drastically. Furthermore, chemical reactions at the interface of the
heterogeneous polymer blend systems can change the phase morphology,

Chapter 1

68

because of their influence on the surface tension of the components,


thereby affecting the interfacial tension and the associated dispersion
effects.
Presuming that only one of the phase of the blends, ie. the elastomer
phase, has to be selectively cross-linked, the changes in the morphology
formation criteria can be characterised as follows.

Viscosity ratio

K d T , J , M d 0
Kc T , J , M c 0

oO

Kd r T , J , M d r
K c T , J , M c 0

..(1.28)

Interfacial tension and melt elasticities

J dc

J dc o  1 / 6 R> V 11  V 22 d  V 11  V 22 @c o

J cr

J dc or  1 / 6 R> V 11  V 22 d r  V 11  V 22 c @

(1.29)

Capillary number
k

K.J .R
o kr
J
dc

K * .J .R r
J dc r

..(1.30)

This is the case during the dynamic vulcanisation of thermoplastic


rubber blends.
Dynamic vulcanisation is characterised by the fact that, the rubber
has to be dispersed into the thermoplastic matrix as fine particles in a
particle size range of about 1m. Such an extraordinary morphology
guarantees the thermoplastic processing behaviour and as well as rubber
like application properties. In dynamic vulcanizates, a cross-liking reaction

Introduction

69

in the dispersed rubber induced a drastic increase in the viscosity of the


phase as well as a significant change in the viscosity ratio, which will affect
the mixing conditions. In TPVs, the previously discussed morphology
formation mechanisms are applicable in the steps prior to the cross-linking,
since a cocontinuous phase morphology occurs in this period.
In order to produce the necessary deformations in a highly viscous
but cocontinuous rubber phase, elongational stresses within an elongatioanl
flow must act on the continuous phase. These deformations are essential on
the one hand for the refinement of the cocontinuous strands and on the
other hand for the initiation of break up of these strands into dispersed
particles during the cross-linking process in this highly deformed state, as
shown in the Fig.1.31.

Figure 1.31: Schematic representation of morphology transformation


during the dynamic vulcanisation of polymer blends
The degree of dispersion, Dr is the ratio of the particle areas before,
A0, and after, A(t), the dispersion process, ie.

Dr

A(t )
A0

(1.31)

Chapter 1

70

The correlation between the viscosity and the degree of dispersion


with respect to time is shown in the Fig.1.32. In Zone-I, a cocontinuous
phase morphology exists. In this zone, the cocontinuous phase will be
deformed by shear and elongational stress. Here, the strands of the
component become thinner. After the addition of the cross-linking agent at
a definite time, the selective cross-linking reaction in the rubber phase is
initiated (Zone II). The viscosity of the rubber and thus the viscosity of the
whole system is strongly increased. With the increase in the viscosity
(jumplike increase in the shear viscosity), the continuous rubber phase was
stretched more and more under shear and elongational stresses. The greater
the number of cross-links in the rubber phase, the greater the load to the
rubber phase. When the critical stress is reached, the continuous rubber
phase cannot deform efficiently and breaks up into small particles. This is
the moment where the cocontinuous morphology is transformed into a
droplet-matrix type morphology.

Figure 1.32: Schematic representation of the course of the viscosity and


degree of dispersion D as functions of time t for a dynamic
vulcanisation process

In zone III, the cross-linked rubber particles now have a very high
viscosity, and further dispersion of these particles by the stress transferred
by the low viscous thermoplastic matrix will be impossible. After the cross-

Introduction

71

linking reaction is completed, only the distribution of the cured particles in


the matrix takes place. The cross linked rubber has got higher surface
tension. Both the cross-linking and the increasing surface tension will
decrease the driving force for coalescence.
One can conclude that the conditions for the formation of fine
particle-matrix morphology are not only a suitable volume fraction and a
viscosity ratio of the components but also, the initial cross linking reaction
of the rubber phase. The volume fraction and viscosity ratio are important
parameters for the formation of a co-continuous phase morphology before
the reaction starts. This cocntinuous structure is an essential condition for
the successful transformation into the fine particle-matrix morphology.
Only the initial continuous phase morphology allows for the effective
loading of shear and elongational stresses on both the thermoplastic and
rubber phases, and this is the necessary condition for the break up for the
rubber phase during the reactive melt mixing or dynamic vulcanisation.
After the cross-linking reaction is completed, only a distribution of the
cured rubber particles in the matrix takes Place.
1.10 Scope and Objective of the Work

Polymers are now widely used in engineering and other fields to


replace conventional materials because of their attractive properties like
light weight, easy processability, corrosion resistance etc. In recent years
the interest has been shifted from pure polymers to mixtures of two or more
polymers in order to tailor the final product to suit specific requirements.
So the thermoplastic elastomers have made a technological breakthrough in
modern times in the field of polymer science and technology. Researchers
are usually more interested in rubber/plastic systems to obtain
thermoplastic elastomer to minimise the gap between elastomer and

Chapter 1

72

plastics. The commercial importances of thermoplastic elastomers are


based on their superior processing properties and economical advantages
over conventional plastics and rubbers.
Thermoplastic elastomers from the blends of nylon copolymer and
EPDM have got special interest. Nylon being used as a substitute for metals,
there is a tremendous practical importance in studying the compatibility and
mechanical properties of nylon based blends. Nylon copolymer used in this
study is a low melting nylon, which exhibits excellent mechanical and thermal
properties but is expensive. Even though nylon based blends have been
extensively studied, this type of low melting nylon is scarcely investigated.
Due to the polar nature, moisture absorption is a serious problem for nylons.
This in turn leads to the dimensional instability of the moulded articles. This
problem can be alleviated by blending with non polar EPDM, which is inert
towards moisture. Ethylene propylene rubbers are one of the cheapest most
widely used and fastest growing synthetic rubbers having both special and
general purpose applications. EPDM rubbers has got excellent resistance to
heat, oxidation, ozone and weather ageing due to their stable, saturated
polymer backbone structure. As a non-polar elastomer it has got good
electrical resistivity.
The blends of nylon copolymer and EPDM are incompatible due to
the difference in the polarity and solubility. To overcome this problem, we
have adopted reactive compatibilisation and dynamic vulcanization.
In this thesis we have systematically studied the effect of
compatibilisation and dynamic vulcanization on the morphology and
properties of nylon copolymer/EPDM blends. It was expected that,
blending of these two polymers would lead to a new cost effective

Introduction

73

polymeric material with good mechanical, thermal and engineering


properties coupled with excellent ozone resistance.
A careful and systematic survey of the literature revealed that no
serious and in depth studies on the morphological changes in the presence
of compatibiliser and crosslinking agents have not been done till date.
Morphological studies were very important since it is the morphology that
determines and controls the ultimate properties of the blends. At the same
time to the best of our knowledge, no research work has been done so far to
investigate the effect of composition, compatibilisation and dynamic
vulcanization of nylon copolymer (which is a copolymer of nylon6 and
nylon 66) and EPDM blend system. Besides we think that there is a great
industrial and commercial future for thermoplastics elastomers, which may
bring a new face to the field of technology.
The above cited experimentally required parameters and the
commercial importance of the new blend systems are the motivations to
select and study the Nylon copolymer /EPDM systems.
The main objectives of the work are:

Preparation of new thermoplastic elastomers from nylon copolymer


and EPDM rubber by melt blending technique.

Reactive compatibilisation of nylon/EPDM blends using compatibiliser,


EPM-g-MA.

Preparation of the crosslinked blends by dynamic vulcanisation.

Evaluation of the phase morphology of uncompatibilised, compatibilised


and dynamically vulcanised blends.

Investigation of the mechanical and dynamic mechanical properties of


the blends.

Chapter 1

74

Analysis of the effects of blend ratio, compatibilisstion and dynamic


vulcanization on the thermal and crystallisation properties of the
blends.

Investigation of the effect of blend ratio, compatibilisation and


dynamic vulcanisation on the rheology of the blends.

Study of the water diffusion of the nylon/EPDM blends and the effect
of compatibilisation, crosslinking and temperature on the diffusion
behaviour.

Analysis of the effect of blending, compatibilisation and crosslinking


on the electrical properties.

Correlating the mechanical, viscoelastic, thermal, crystallization,


rheological, transport and electrical properties of the blends with the
phase morphology in presence and absence of compatibiliser and
crosslinking agents.

Comparison of the experimental results with the theoretical predictions.

Introduction

75

1.11 References
1.

J. A. Manson and L.H Sperling, Polymer blends and Composites.


Plenum Press. New York.1976.

2.

D.R Paul and S. Newman. (Eds). Polymer Blends. Vol. II and I.


Academic Press. New York 1978.

3.

M.T Shaw, Poly. Eng. Science. 22, 115, 1982.

4.

L. M. Robeson, Poly. Eng. Sci. 24, 587, 1984.

5.

L. A. Utracki, Polymer Alloys and Blends-Thermodynamics and


Rheology, Hanser Publishers, Munich, 1990.

6.

P. Ghosh, Polymer Science and Technology, Plastics, Rubbers / Blends


and Composites, Second edition, Tata Mc Graw-Hill Publishing
Company Ltd., New Delhi, 2002.

7.

B.M. Walker, editor, Handbook of thermoplastic elastomers, New


York, Van Nostrand Reinhold, 1979.

8.

S. K. De, A. K. Bhowmick, editors. Thermoplastic elastomers from


rubber plastic blends, Chichester, UK: Ellis Horwood 1990.

9.

N. R. Legge, G.Holden and H.E Schroeder (Eds). Thermoplastic elastomer.


A comprehensive Review, Hanser Publishers. Munich, 1987.

10.

H. L. Morris, Hand book of Thermoplastic Elastomers Van Nostrand


Reinhold, New York, 1979.

11.

B. M. Walker and C.P Rader (Eds), Hand book of Thermoplastic


Elastomers, Van Nostrand Reinhold, New York, 1988.

12.

A. K. Bhowmick and H.L Stephens (Eds), Handbook of Elastomers:


New developments and Technology, Marcel Dekker, New, York,
1988.

Chapter 1

76

13.

ASTM D. 5593-99: Standard Classification for Thermoplastic


Elastomers Olefinic (TEO)

14.

ASTM D 5046-98: Standard specification for Fully Crosslinked


elastomeric Alloys.

15.

D. S. Rosa Rosa, C.G.F Guedes., Polym. Test. 26, 209, 2007.

16.

R. Sonnier, E. Leroy, Polym. Test. 26, 274, 2007.

17.

Z H.S Moon, S Hyun, W.M Choi, J Appl. Polym. Sci. 104, 95, 2007.

18.

N. Li, M.J Kontopoulou, Polym. Eng. 26, 633, 2006.

19.

Y.J Li, Y. Oono., Nakayama, K, H.Shimizu. Macromol. Mater. Eng.


291, 1201, 2006.

20.

W. S. Wang, P. Ping, H. J Yu, J. Polym. Scipol. Chem. 44, 5505, 2006.

21.

Y. W. Chang, J. K Mishra, S. K Kim, Mater. Lett. 60, 3118, 2006.

22.

Y. J. Li, Y. Kadowaki, T. Inoue, Macromolecules 39, 4195, 2006.

23.

L. L. Hou, H. Z. Liu, G. S. Yang, Polym. Iny. 55, 643, 2006.

24.

S. Toki, I. Sics, C. Burger, Macromolecules 39, 3588, 2006.

25.

J. George, N. R. Neelakantan, K. T. Varughese, J. Appl. Polym. Sci. 100,


2912, 2006.

26.

H.Z. Liu, T.X. Xie, Y. Zhang, J. Polym. Sci. Polym. Phys. 44, 1050, 2006.

27.

S.L. Zhang, G. B. Wang, Z. H Jiang, J. Polym. Sci. Polym. Phys. 43,


1177, 2005.

28.

T. Asami, K. Nitta, Polymer 45, 5301, 2004.

29.

T. X. Xie, G.S. Yang, J. Appl. Polym. Sci. 93, 1446, 2004.

30.

Halimatuddahliana, H. Ismail, Polym. Plast. Technol. 43,357, 2004.

31.

Y.C. Ou, Y.G Lei, X. P Fang, J. Appl. Polym. Sci. 91,1806,2004.

Introduction

77

32.

F. Dobry, Boyer-Kawenoki, J. Polym. Sci., 2, 90, 1947.

33.

S. Krause, J. Macromol. Sci. C: Rev. Macromol. Chem., 7, 251, 1972.

34.

S. Krause, in Polymer Blends, Vol. 1, D.R. Paul, S. Newman, Eds.,


Academic Press, New York, 1978.

35.

S. Krause, in Polymer Handbook, J. Brandrup, E.H. Immergut, Eds.,


3rd Ed., Wiley Interscience, New York, 1989.

36.

S. Krause, S.H. Goh, in Polymer Handbook, J. Brandrup, E.H.


Immergut, E.A. Grulke, Eds. 4th Ed., Wiley Interscience, New York,
1999.

37.

L.A. Utracki, in Polymer Blends Handbook, L.A. Utracki, Ed., Volume


1, Kluwer, Academic Publishers, Dordrecht, 2002.

38.

G.D. Merfeld, D.R. Paul, in Polymer Blends, Vol.1, D.R. Paul, C.B.
Bucknall, Eds, Wiley Interscience, New York, 2000.

39.

R.L. Scott, J. Chem. Phys., 17, 279, 1949.

40.

H. Tompa, Trans. Faraday Soc.45, 1142, 1949.

41.

P.J. Flory, R.A. Orwoll, A.Vrij, J.Am.Chem.Soc., 86, 3507, 1964.

42.

J. T. Dee and D. J. Walsh, 21, 811, 1988.

43.

J. H. Hildebrand and R.L Scott, Reinhold, New York, 1950.

44.

P.C. Painter, Y. Park., M.M Coleman, Macromolecules, 22, 570, 1989.

45.

D.R. Paul and C.B Bucknall., Introduction in polymer blends, Vol.1


John Wiley & Sons, New York, pp.1-14, 1999.

46.

J. Noolandi, Polym. Eng. Sci. 24, 70, 1984.

47.

R. Ashaletha, S. Thomas, M.G. Kumaran, Rubber Chem. Technol., 68, 671,


1995.

Chapter 1

78

48.

R. Ashaletha, G. Groeninckx, M.G. Kumaran, S. Thomas, Polym. Plast.


Technol. Eng., 34, 653, 1995.

49.

R. Ashaletha, M.G. Kumaran, S. Thomas, Polym. Degrad. Stab., 61, 431,


1998.

50.

R. Ashaletha, G. Groeninckx, M.G. Kumaran, S. Thomas, J. Appl. Polym.


Sci., 69, 2673, 1998.

51.

R. Ashaletha, M.G. Kumaran, S. Thomas, Eur. Polym. J., 35, 253, 1999.

52.

Z. Oommen, S. Thomas, Polym. Bull., 31, 623, 1993.

53.

Z. Oommen, M.R.G. Nair, S. Thomas, Polym. Eng. Sci., 36, 151, 1996.

54.

Z. Oommen, S. Thomas, J. Appl. Polym. Sci., 65, 1245, 1997.

55.

Z. Oommen, S. Thomas, J. Mater. Sci., 32, 6085, 1997.

56.

Z. Oommen, C.K. Premaletha, B. Kuriakose, S. Thomas, Polymer, 36, 561,


1997.

57.

Z. Oommen, G. Groeninckx, S. Thomas, J. Polym. Sci. B: Polym. Phys.


38, 525, 2000.

58.

S. Thomas, R.E. Prodhomme, Polymer, 33, 4260, 1992.

59.

S. George, R. Joseph, S. Thomas, K.T. Varughese, Polymer, 36, 4405,


1995.

60.

S. George, L. Prasannakumari, P. Koshy, K.T. Varughese, S. Thomas,


Mater. Lett., 26, 51, 1996.

61.

S. George, N.R. Neelakantan, K.T. Varughese, S. Thomas, J. Polym. Sci. B:


Polym. Phys., 35, 2309, 1997.

62.

S. George, R. Ramamurthy, J.S. Anand, G. Groeninckx, K.T. Varughese, S.


Thomas, Polymer, 40, 4325, 1999.

63.

S. George, K.T. Varughese, S. Thomas, Polymer, 41, 5485, 2000.

Introduction

79

64.

M. Mathew, S. Thomas, Polymer, 44, 1295, 2003.

65.

J. George, S. George, S. Thomas, Int. Plast. Eng. Technol., 1, 15, 1994.

66.

J. George, R. Joseph, S. Thomas, K.T. Varughese, J. Appl. Polym.


Sci., 57, 449, 1995.

67.

J. George, L. Prasannakumari, P. Koshy, K.T. Varughese, S. Thomas,


Polym. Plast. Technol. Eng., 34, 561, 1995.

68.

J. George, K. Ramamurthy, K.T. Varughese, S. Thomas, J. Polym. Sci.


B: Polym. Phys., 38, 1104, 2000.

69.

S. Joseph, Z. Oommen, S. Thomas, Mater. Lett., 53, 268, 2002.

70.

S. Joseph, F. Laupretre, C. Negrell, S. Thomas, Polymer, 46, 9385, 2005.

71.

C.R. Kumar, S.V. Nair, K.E. George, Z. Oommen, S. Thomas, Polym.


Eng. Sci., 43, 9, 2003.

72.

C.R. Kumar, I. Aravind, R. Stephan, P. Koshy, J. Jose, H.J. Radusch,


H. G.H. Michler, R.R. Varma, S. Thomas, Prog. Rubber Plast. Recycl.
Technol., 21, 277, 2005.

73.

S.V. Nair, M.G. Kumaran, S. Thomas, J. Appl. Polym. Sci., (Submitted).

74.

S.V. Nair, B. Francis, M.G. Kumaran, S. Thomas, J. Polym. Sci. B:


Polym. Phys., (Submitted).

75.

B. John, K.T. Varughese, Z. Oommen, P. Potschke, S. Thomas, J.


Appl. Polym. Sci., 87, 2083, 2003.

76.

K. A. Moly, Z. Oommen, S.S. Bhagawan, G. Groeninckx, S. Thomas,


J. Appl. Polym. Sci. 86, 3210, 2002.

77.

K. A. Moly, S.S. Bhagawan, S. Thomas, Mater. Lett., 53, 346, 2002.

78.

K. A. Moly, H.J. Radusch, R. Androsh, S.S. Bhagavan, S. Thomas,


Eur. Polym. J., 41, 1410, 2005.

Chapter 1

80

79.

Z. Oommen, G. Groeninckx, S. Thomas, J. Appl. Polym. Sci., 92, 252,


2004.

80.

Z. Oommen, S.R. Zachariah, S. Thomas, I. Aravind, G. Groeninckx, J.


Macromol. Sci., B: Phys., 43, 1, 2004.

81.

S. Thomas, G. Groeninckx, Polymer, 71, 1405, 1999.

82.

S. Jose, B. Francis, S. Thomas, Macromolecules, (submitted).

83.

S. Jose, P. Koshy, S. Thomas, J. Karger-Kocsis, J. Polym. Sci. B:


Polym. Phys., (accepted).

84.

S. Jose, B. Francis, S. Thomas, J. Karger-Kocsis, Polymer, (In press).

85.

S. Jose, S.V. Nair, S. Thomas, J. Karger-Kocsis, J. Appl. Polym. Sci.,


99, 2640, 2006.

86.

I. Aravind, P. Albert, P. Ranganathaiah, J.V. Kurian, S. Thomas,


Polymer, 45, 4925, 2004.

87.

W.J. Coumans, D. Heikens, S.D. Sjoerdsma, Polymer, 21, 103, 1980.

88.

D. Heikens, N. Hoen, W.M. Barentsen, P.Piet, H.Ladan, J. Polym. Sci.,


Polym. Symp., 62, 309, 1978.

89.

D.R. Paul and S.Newman (Eds)Polymer Blends.Chap12, Academic


Press, New York, 1978.

90.

R. Fayt, R. Jerome and P.H.Teyssie, J. Polym. Sci., Polym. Lett. Ed., 24,
25, 1981.

91.

N Chapleau, B. D. Favis, P. Carreau. J. Polym. Sci. Polym. Phys., 36,


1947, 1998.

92.

G. E Molau, J. Polym. Sci., 13, 1267, 1965.

93.

G. E. Molau, J. Polym.Sci., 13, 4235,1965.

94.

G. E Molau, W. M Wittbrodt, Macromolecules, 1,260,1968.

Introduction

95.

81

G. Riess, J. Kohler, C. Tournut, A. Banderet, Makromol. Chem., 101,


58, 1967.

96.

J. Kohler, G. Riess, A. Banderet, Eur. Polym. J., 4, 173, 1968.

97.

G. Riess, Y. Jolivet, Am. Chem. Soc. Adv. Chem. Ser., 142, 243, 1975.

98.

J. Periard, G. Riess, Colloid Polym. Sci., 253, 362, 1975.

99.

P. Gailard, M. Ossenbach-Santer, G. Riess, Makromol. Chem. Rapid.


Commun., 1, 771, 1980.

100. T. Inoue, T. Soen, T. Hashimoto, H. Kawai, Macromolecules, 3, 87, 1970.


101. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Lett. Ed., 19, 79,
1981.
102. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Phys. Ed., 19,
1269, 1981.
103. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Phys. Ed., 20,
2209, 1982.
104. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Chem. Ed., 23,
337, 1985.
105. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Lett. Ed., 24,
25, 1986.
106. R. Fayt, R. Jrme, Ph. Teyssi, Makromol. Chem., 187, 837, 1986.
107. R. Fayt, R. Jrme, Ph. Teyssi, J. Polym. Sci. Polym. Phys. Ed., 27,
775, 1989.
108. D. Heikens, W.M. Barentsen, Polymer, 14, 579, 1973.
109. D. Heikens, W.M. Barentsen, P. Piet, Polymer, 15, 119, 1974.
110. D.R. Paul, G.E. Locke, J. Appl. Polym. Sci., 17, 2597, 1973.

Chapter 1

82

111. D.R. Paul, G.E. Locke, J. Appl. Polym. Sci., 17, 2791, 1973.
112. D.R. Paul, C.R Lindsey, J.W.Burton, J. Appl. Polym. Sci., 26, 1,1981.
113. B.G. Soares, A.S. Sirqueria, M.G. Oliveira, M.S.M Almeida, Macromol.
Symp., 189, 45, 2002.
114. D.F. Ferrari and W.E Baker, J. Polym. Sci. Part A: Polym. Chem., 36,
1572, 1998.
115. W.B. Baker, C.E Scott, G.H.Hu eds., Reactive Polymer Blending,
Hanser, Munich, 2001.
116. C.G. Hagberg, J.L. Dickerson, J.L Plast. Eng. 53, 41,1997.
117. J. Xueliang, Z. Yong; Z. Yinxi. J. Polym. Sci., Part B: Polym. Phy. 42,
1181, 2004.
118. R.Gadekar, A.Kulkarni, J.P Jog, J. Appl. Polym. Sci. 69, 161,1998.
119. C. Pagnoulle, R.Jerome, Polyblends 97, Brookfield, 7,1997.
120. Y. Seo, J. Appl. Polym. Sci., 64, 359, 1997.
121. C.C. Chen, J.L.White, Polym. Eng. Sci., 33,923,1993.
122. S. Balakrishnan, N.R. Neelakandan, D.N. Saheb, J. Pjog, Polymer, 39,
5765, 1998.
123. J.R.J. Campbell, S.Y.Hobbs, T.J. Shea, V.H. Whatkins, Polym. Eng.
Sci., 30, 1056, 1990.
124. D. Maeder, J. Kressler, M. Weber, Macromol. Symp., 112, 123,1996.
125. S.A. Madbouly, J.U. Otaigbe, T.Ougizawa, Macromol. Chem. Phys.,
207, 1233, 2006.
126. S.L. Sun, Z.Y. Tan, M.Y. Zhang, Polym. Int., 55, 834, 2006.
127. Y. Li, T. Xie, G. Yang, J. Appl. Polym. Sci., 95, 1354, 2005.

Introduction

83

128. G. Hu, B. Wang, X. Zhou, Polym. Int., 54, 316, 2005.


129. A.R. Bhattacharyya, A.K. Ghosh, A. Misra, K.J. Eichhorn, Polymer,
46, 1661, 2005.
130. S.M. Lai, Y.C. Liao, T.W. Chen, Polym. Eng. Sci., 45, 1461, 2005.
131. H.K. Jeon, J. Zhang, C.W. Macosko, Polymer, 46, 2422, 2005.
132. Y. Seo, T.H. Ninh, Polymer, 45, 8573, 2004.
133. M.G. Oliveira, B.G Soares, J. Appl. Polym. Sci., 90, 2408, 2003.
134. E.M Araujo, E Hage, A.J.F Carvalho, J. Mater. Sci., 38, 3515, 2003.
135. X. Liu, H. Huang, Y. Zhang, Polym. Compos., 11, 179, 2003.
136. X.Q. Zhang, Y. Son, J. Appl. Polym. Sci., 89, 2502, 2003.
137. C. Pagnoulle, R. Jrme, Polymer, 42, 1893, 2001.
138. J. Roeder, R.V.B. Oliveira, M.C. Goncalves, V. Soldi, A.T.N. Pires,
Polym. Test., 21, 815, 2002.
139. K.J. Kim, H.W. Cho, K.J. Yoon, Eur. Polym. J., 39, 1249, 2003.
140. G. Wildes, H. Keskkula, D.R. Paul, Polymer, 40, 5609, 1999.
141. R.A. Kudva, H. Keskkula, D.R. Paul, Polymer, 41, 239, 2000.
142. R.A. Kudva, H. Keskkula, D.R. Paul, Polymer, 41, 335, 2000.
143. X. Zhang, Z. Yin, J. Yin, J. Appl. Polym. Sci., 62, 893, 1996.
144. C.R. Chang, F.C. Chang, J. Appl. Polym. Sci., 61, 2411, 1996.
145. E.G. Koulouri, A.X. Georgaki, J.K. Kallitsis, Polymer, 38, 4185, 1997.
146. Z. Xiaomin, Y. Zhihui, N. Tainhai, Y. Jinghua, Polymer, 38, 5905, 1997.
147. Z. Xiaomin, L. Gang, W. Dongmei, Y. Zhihui, Y. Jinghua, L. Jingshu,
Polymer, 39, 15, 1998.

Chapter 1

84

148. R.A. Kudva, H. Keskkula, D.R. Paul, Polymer, 39, 2447, 1998.
149. A. Tedesco, R.V. Barbosa, S.M.B. Nachtigall, R.S. Mauler, Polym.
Test., 21, 11, 2002.
150. V. Chiono, S. Filippi, H. Yordanov, L. Minkova, P. Magagnini,
Polymer, 44, 2423, 2003.
151. J.K. Kim, S. Kim, C.E. Park, Polymer, 38, 1809, 1997.
152. J.K. Kim, S. Kim, C.E. Park, Polymer, 38, 2155, 1997.
153. J.K. Kim, D.K. Yee, H.K. Jeon, C.E. Park, Polymer, 40, 2739, 1999.
154. W. Hale, H. Keskkula, D.R. Paul, Polymer, 40, 365, 1999.
155. B.K Kim, S.Y Park, S.J Park, Eur. Polym. J., 27, 349, 1991.
156. M.L. Xue, Y.L. Yu, J. Sheng, H. H. Chuah, C-H. Geng, J. Macromol.
Sci. Part B: Phys., 44, 317, 2005.
157. C.Vocke, U. Antilla, J. Seppala, J. Appl. Polym. Sci., 72, 1443, 1999.
158. S.C. Jana, N. Patel, D. Dharaiya, Polymer, 42, 8681, 2001.
159. C. Koning, M. Van Duin, C. Pagnoulle, R. Jrme, Prog. Polym. Sci., 23,
707, 1998.
160. P.S. Archondouli, N.K. Kalfoglou, Polymer, 42, 3489, 2001.
161. D.A. Costa, C.M.F. Oliveira, J. Appl. Polym. Sci., 81, 2556, 2001.
162. A. Retolaza, J.I. Eguiazabal, J. Nazabal, J. Appl. Polym. Sci., 97, 564, 2005.
163. T.G. Gopakumar, S. Ponrathnam, A. Lele, C.R. Rajan, A. Fradet,
Polymer, 40, 357, 1999.
164. H.Q. Xie, Y. Chen, W. Yang, D. Xie, J. Appl. Polym. Sci., 101, 792, 2006.
165. Y. Li, B.Y. Zhang, Z. Feng, A. Zhang, J. Appl. Polym. Sci., 83, 2749, 2002.
166. B.D.Favis, J.M Willis, J. Polym. Sci. Polym. Phys., 28, 2259,1990.

Introduction

85

167. B. Majumdar, D.R. Paul, A.J. Oshinski, Polymer, 38, 1787, 1997.
168. A.J. Oshinski, J.H. Keskkula, D.R. Paul, Polymer, 33, 284, 1992.
169. B. Majumdar, H. Keskkula, D.R. Paul, N.G. Harvey, Polymer, 35,
4263, 1994.
170. A. Gonzalez-Montiel, J.H. Keskkula, D.R. Paul, Polymer, 36, 4587,
1995.
171. A.J. Oshinski, H. Keskkula, D.R. Paul, Polymer, 37, 4909, 1996.
172. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 1386, 1994.
173. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 1399, 1994.
174. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 3164, 1994.
175. A. Gonzalez-Montiel, A.J. Oshinski, H. Keskkula, D.R. Paul, J. Polym.
Sci. B: Polym. Phys., 33, 1751, 1995.
176. W. Loyens, G. Groeninckx, Macromol. Chem. Phys., 203, 1702, 2002.
177. A. Gonzalez-Montiel, J.H. Keskkula, D.R. Paul, Polymer, 36, 4587, 1995.
178. K. Dedecker, G. Groeninckx, Polymer, 39, 5001, 1998.
179. G. Groeninckx, C. Harrats, S. Thomas, Reactive Polymer Blending,
Eds. W.E. Baker, C.E. Scott, G.H. Hu, Hanser, Munich, 2001.
180. K. Dedecker and G. Groeninckx, J. Appl. Polym. Sci., 73, 889, 1999.
181. I. Fortenly, Z. Cerna, J. Binho, J. Kovar, J. Appl. Polym. Sci., 48, 1731,
1993.
182. K.M. Hong, J. Noolandi, Macromolecules, 13, 964, 1980.
183. K.M. Hong, J. Noolandi, Macromolecules, 14, 727, 1981.
184. K.M. Hong, J. Noolandi, Macromolecules, 14, 736, 1981.

Chapter 1

86

185. D. Broseta, L. Leibler, L.O. Kaddour, C. Strazielle, J. Chem. Phys., 87,


7248 1987.
186. J. Noolandi, Polym. Eng. Sci., 24, 70, 1984.
187. J. Noolandi, B. Bunsenges, Phys. Chem., 89, 1147, 1985.
188. L. Leibler, Macromolecules, 13, 1602, 1980.
189. L. Leibler, Makromol. Chem. Macromol, Symp., 16, 1, 1988.
190. T.A. Vilgis, J. Noolandi, Makromol. Chem., Makromol. Symp., 16.
225, 1988.
191. H. Anastasiadis, I.S. Gancarz, J.T. Koberstein, Macromolecules, 21,
2980, 1988.
192. L.A. Utracki, Z.H. Shi, Polym. Eng. Sci., 32, 1824, 1992.
193. T. Tang, B. Huang, Polymer, 35, 281, 1994.
194. D.R. Paul, in Polymer Blends, Vol 2, D.R. Paul, S. Newman, Ed.,
Academic Press, New York, 1978.
195. M. Matos, F. D Favis, Master thesis, Ecole Polytechnique de Montral,
1993.
196. P. Lomellini, M. Matos, B.D. Favis, Polymer, 37, 5689, 1996.
197. M. Gessler. Process for preparing a vulcanized blend of crystalline
polyporpylene and chlorinated butyl rubber, US patent 3, 037, 954,
1962.
198. K. Fisher, Thermoplastic blend of partially cured mono olefin copolymer
rubber and polyolefin plastic, US Patent 3, 758, 643, 1973.
199. A. Y. Coran, R. P. Patel Rubber thermoplastic compositions Part I.
Chem. Technol., 53,141,1980.

Introduction

87

200. A. Y. Coran, R. P. Patel, Williams Drubber - Thermoplastic compositions


Part V., Rubber chem. Technol., 64,769, 1991.
201. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 53,141,1980.
202. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 53, 781,1980.
203. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 53,91,1980.
204. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 53, 892, 1980.
205. A.Y. Coran, R.P. Patel and D. Williams, Rubber Chem. Technol., 55,
116, 1982.
206. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 56, 210,1983.
207. A.Y. Coran, R.P. Patel. Rubber Chem. Technol., 56, 1045, 1983.
208. X. Liu, H. Huang, Z.Y. Xie, Y. Zhang, Y.X. Zhang, K. Sun, L.N. Min,
Polym. Testing, 22, 9, 2003.
209. N. Kinsuk; W. Noordermeer, M. Jacques. Rubber Chem. and Tech. 77,
955, 2004.
210. S. Sararoudi, H.Nazockdast, A.A Katbab,. Rubber Chem. and Tech.
77, 847, 2004.
211. P. Martin, C. Maquet, R. Legras, C. Bailly, L. Leemans, M. Van Gurp,
M. Van Duin, Polymer, 45, 5111, 2004.
212. A. Verbois, C. Philippe; M. Alain, G. Jacques, R. Claude. Polym. Inter.,
53, 523, 2004.
213. F. Riahi, Benachour, Djafer, Douibi, Abdelmalek Inter.J.Polym.
Materials, 53, 143, 2004.
214. H. Ismail and H. Akil, Inter. J. Polym. Mater., 54, 1169, 2005.
215. N. Charoen, T. Akarapong, K. Azizon. J. Appl. Polym. Sci. 98, 1251, 2005.

Chapter 1

88

216. M. Ahmad, Inter. J. Polym. Materi., 54, 619, 2005.


217. C.Joubert, L. Choplin, A. Michel, P. Cassagnau, J. Polym. Eng., 25, 59,
2005.
218. M. Ahmad, U.S. Ishiaku, Z. A. Mohd Ishak, Polym. Bulletin, 53, 203,
2005.
219. H. Supri, Ismail., Polym. Testing, 25, 318, 2006.
220. M. Van Duin, , Macromolecular Symposia 233, 11, 2006.
221. C. Nakason, P. Wannavilai, A, J. Kaesaman. J. Appl. Polym. Sci., 100,
4729, 2006.
222. J. George, N. R. Neelakantan, K. T. Varughese, S. Thomas, J. Appl.
Polym. Sci., 100, 2912, 2006.
223. D. Romanini, E. Garagnani, E. Marchetti, New Polym. Mat. Proc. Int.
Seminar, 56, 40, 1987.
224. Y. Kikuchi, T. Fukui, T. Okada, T. Inoue, Polym. Eng. Sci., 31, 1029,
1991.
225. S. Abdou and K. Shen, Monsanto Co., 4, 594,1982.
226. W. K. Fischer, U. S Pat. 3, 758.643,1973.
227. W. K. Fischer, U. S Pat. 3, 835.201,1974.
228. W. K. Fischer, U.S Pat. 3, 862.106,1975.
229. K. Naskar, J.W.M Noordermeer, Rub. Che. and Tech., 77,955,2004.
230. C. Radhesh Kumar, S. Thomas, Progress in Rubber, Plastics and
Recycling Technology, 21, 277, 2005.
231. O. P. Grigoryeva, A. M., Fainleib, A. L. Tolstov, O. M. Starostenko, E.
Lievana, J.Karger-Kocsis, J. Appl. Polym. Sci., 95, 659, 2005.

Introduction

89

232. C. Nakason, S. Saiwari, A. Kaesaman, Polym. Eng. and Sci., 46, 594, 2006.
233. H. Huang, T. Ikehara, T. Nishi, J. Appl. Polym. Sci., 90, 1242, 2003.
234. J. Oderkerk, G. Groeninckx, Polymer, 43, 2219, 2002.
235. J. Oderkerk, G. Groeninckx, M. Soliman, Macromolecules, 35, 3946,
2002.
236. J. Oderkerk, G. De Schaetzen, B. Goderis, L. Hellemans, G.
Groeninckx, Macromolecules, 35, 6623, 2002.
237. L.A. Utracki, in Polymer Blends Handbook, L.A. Utracki, Ed., Volume
1, Kluwer, Academic Publishers, Dordrecht, The Netherlands, 2002.
238. C.W. Macoscko, Macromol. Symp., 149, 171, 2000.
239. D. R. Paul, in polymer blends, D. R. Paul and Newman, s. Eds., Academic
Press, New York, 1978.
240. H. F. Mark, M. Bikales, C. G. Over Berger, G. Menges, J.I Kroschwitz,
Eds., Encyclopaedia of Polymer Science and Engineering, 2nd Ed., John
Wiley & Sons, New York, 1987.
241. D. R. Paul and C. B. Bucknall, Eds., Polymer Blends John Wiley &
Sons, New York, 2, 2000.
242. J.J. Elmendorp, Ph.D Thesis, Technical University, Delft, The
Netherlands, 1986.
243. H.J. Van Oene, J. Colloid interface Sci., 40, 448, 1972.
244. J. Lyngaae-Jorgensen, Org. Coat. Plast. Chem., 15, 174, 1981.
245. L.A. Utraki, Z. H. Shi, Polym. Eng. Sci., 32, 1824, 1992.
246. H.P. Grace, Chem., Eng., Commun., 14, 225, 1982.
247. F.D. Rumscheid and S. G. Mason, J. Colloid Sci., 16, 238, 1961.

Chapter 1

90

248. C.E. Scott, C. W. Macosko, Polym. Bull., 26, 341, 1991.


249. C.E. Scott, C. W. Macosko, Polymer, 36, 461, 1995.
250. U. Sundararaj, C. W. Macosko, A. Nakayama, T. Inoue, Polym. Eng.
Sci., 35, 100, 1995.
251. U. Sundararaj, Y. Dori, C.W. Macosko, Polymer, 36, 1957, 1995.
252. U. Sundararaj, Y. Dori, C. W. Macosko, SPE Tech. Papers, 52, 2448,
1994.
253. L. Levitt, C. W. Macosko, S. D. Pearson, Polym. Eng. Sci., 36, 1647,
1996.
254. N. D. B. Lazo, C. E Scott, Polymer, 40, 5469, 1999.
255. N. D. B. Lazo, C.E Scott, Polymer, 42, 4219, 2001.
256. V. Cristini, R. WHooper, C. W. Macosko, M. Simeone, S.Guido, Ind.
Eng. Chem. Res., 41, 6305,2002.
257. B.Lin, U.Sundararaj, F.Mighri, M.A Huneault, Macromol. Rapid.
comm., 24, 783, 2003.
258. Y. Yang, L.J Lee, K.W. Koelling, Polymer, 45, 1959, 2004.
259. B. Lin, U. Sundararaj, Polymer, 45, 7605, 2004.
260. U. Sundararaj, R.J. Roland, H.T. Chan, C.W. Macosko, Polym. Eng.
Sci., 32, 1814, 1992.
261. J.T. Lindt and A.K. Ghosh, Polym.Eng. Sci., 32, 1802,1992.
262. U. Sundararaj, C.W. Macosko, C.K. Shih, Polym. Eng. Sci., 36, 1769,
1996.
263. L.Levitt, C.W. Macosko, Macromolecules. 32,6270,1999.

Introduction

91

264. C. W. Macosko, P. Guegan, A. K. Khandpur, A. Nakayama, P. Marechal,


T.Inoue, Macromolecules, 29, 5590,1996.
265. J.H.M. Janssen and H.E.H. Meijer, Polym. Eng. Sci. 35, 1766, 1995.
266. P.H.M. Elemans, H.L Bos, J.H.M. Janssen, Chem. Eng. Sci., 48, 267,
1993.
267. C.K. Shih, D. G. Tynan D. A. Denelsbeck, Polym. Eng. Sci., 31, 1670,
1991.
268. B.D. Favis, J. Appl. Polym. Sci. 39, 285, 1990.
269. V. Bourdereau, Z. H Shi, L. A Utraki, P. Sammit P, M. Carrega,
Polym. Eng. Sci., 32, 1846, 1992.
270. P. Ghodgaonkar, U. Sundararaj, Polym. Eng. Sci., 36, 1656, 1996.
271. B.D. Favis and J.P. Califoux Polym. Eng. Sci., 27, 1591, 1987.
272. H. Li, G.H Hu, J.A Sousa, J. Polym. Sci. Polym. Phys., 37, 3368,1999.
273. D. Bourry, B.D. Favis, Polymer, 39, 1851, 1998.
274. U. Sundararaj, Ph.D thesis, University of Minnesota, Minneapolis,
MN, 1994.
275. R.C. Willemse, E.J.Jramaker, J.Van Dam A.P. De Boer, Polymer, 40,
6651, 1999.
276. R. Ratnagiri, C.E. Scott, Polym. Eng. Sci., 41, 1310, 2001.
277. C.K. Shih, Polym. Eng. Sci., 35, 1688, 1995.
278. U. Sundararaj, Macromol. Symp, 85, 112, 1996.
279. R. Ratnagiri, C.E Scott, Polym. Eng. Sci., 38, 1751, 1998.
280. R. Ratnagiri, C.E. Scott, C.K Shih, Polym. Eng. Sci., 41, 1019, 2001.
281. H.E. Burch, C.E. Scott, Polymer, 42, 7313, 2001.

Chapter 1

92

282. D.R. Paul, J.W. Barlow, J.Macromol. Sci.-Rew., Macromol. Chem.,


18, 109, 1980.
283. G.M. Jordhamo, J. A.Mason, Polym. Eng. Sci., 26, 517, 1986.
284. I.M. Krieger and T.J. Dougherty, Trans. Soc. Rheol., 3, 137,1959.
285. J.M.H. Janssen, Dynamics of liquid-liquid mixing, Wiley, New York,
115, 1997.
286. C.E. Scott, S.K. Joung, Polym. Eng. Sci., 36, 1666, 1996.
287. L.A. Utracki and Z.H. Shi Polym. Eng. Sci., 32, 1824, 1992.
288. N.Tokita, Rubber, Chem. Technol., 50, 292, 1977.
289. J. Karger-Kocsis, A. Kallo, A.Szafner, G.Bodor, Z.Senyei, Polymer,
19, 448, 1978.
290. H.P. Schrieber and A.Olguin, Polym. Eng. Sci., 23, 129, 1983.
291. A.P. Plochocki, S.S. Dagli and R.D. Andrews, Polym. Eng. Sci., 30,
741, 1990.
292. S. Wu, Polym. Eng. Sci., 27,335, 1987.
293. B.D. Favis and J.P. Chalifoux, Polym. Eng. Sci., 27, 1591, 1987.
294. C.M. Ronald and G.G.A. Bohm, J. Polym. Sci. Polym. Phys., 22, 79,
1984.
295. J.J. Elmendorp and A.K. Van der Vegt, Polym. Eng. Sci., 26, 1332,
1986.
296. J. Lyngaae-Jorgensen and A.Valenza, Makromol. Chem. Macromol.
Symp., 38, 43,1990.
297. H.B. Chin and C.D. Han, J.Rheol., 24,1,1980.
298. K. Min, J.L. White and J.F. Fellers, J. Appl. Polym. Sci., 29, 2117,1984.

Introduction

93

299. P. Charoensirisomboon, T.Inoue, S.I. Solomko, G.M Sigalov, M. Weber,


Polymer, 41,7033, 2000.
300. G.E. Schulenburg, Foddering, G.Ingenbleek, Polymer, 39, 765, 1998.
301. N. Grizzuti and O.Bifulco, Rheol. Acta, 36, 406, 1997.
302. S.P. Lyu, F.S. Bates, C.W. Macosko, AIChE J.46, 229, 2000.
303. S.P. Lyu, F.S. Bates, C.W. Macosko, AIChE J.48, 7, 2002.
304. S.P. Lyu, F.S. Bates, C.W. Macosko, Macromolecules, 35, 7855, 2002.
305. P. Van Puyvelde, S. Velankar, J. Mewis, P. Moldenaers, Polym. Eng.
Sci., 42, 1956, 2002.
306. J.C. Lepers, B.D. Favis, C.Lacroix, J. Polym. Sci. Polym. Phys., 37, 939,
1999.
307. H. Yang, C.C. Park, Y.T. Hu, L.G. Leal, Phys. Fluids, 13, 1087, 2001.
308. J.W. Ha, Y.Yoon, L.G. Leal, Phys. Fluids, 15, 849, 2003.
309. L.G. Leal, Phys. Fluids, 16, 1833, 2004.
310. I. Fortelny and J. Kovar, Polym. Compos., 9, 119,1988.
311. I. Fortelny and A. Zivny, Polymer, 36, 4113, 1995.
312. I. Fortelny and A. Zivny, Polymer, 39, 2669, 1998.
313. U. Sundararj and C.W. Macosko, Macromolecules, 28, 2647, 1995.
314. R. Fayt, R. Jerome, P. Teyssie, J. Polym. Sci. Poly. Phys., 27, 775, 1989.
315. C. Harrats, S.Blacher, R.Fayt, R.Jerome, P.Teyssie, J. Polym. Sci.
Poly. Phys., 33, 801, 1995.
316. M. Maric and C.W Macosko, Poly. Eng. Sci., 41, 118, 2001.
317. B.D. Favis, Polymer, 35, 1552, 1994.

Chapter 1

94

318. M. Matos, B.D. Favis, P.Lomellini, Polymer, 36, 3899, 1995.


319. P. Lomellini, M. Matos, B.D. Favis, Polymer, 37, 5689, 1996.
320. S. Thomas, G. Groeninckx, Polymer, 49, 5799, 1999.
321. R.T. Tol, G. Groeninckx, I.Vinckier, P.Moldenaers, J. Mewis, Polymer, 45,
2587, 2004.
322. S. Thomas, G. Groeninckx, J. Appl. Polym. Sci., 71, 1405, 1999.
323. S.T. Milner, H.W Xi, J. Rheol., 40, 663, 1996.
324. B.D. Favis and J. P. Chalifoux, Polymer, 29, 1761, 1988.
325. Y.G. Cho and M.R. Kamal, Polym. Eng. Sci., 42, 2005, 2002.
326. G.I. Taylor, Proc. R. Soc. Londen, A138, 41, 1932.
327. G.I. Taylor, Proc. R. Soc. A146, 501, 1934.
328. V. Evaraert, L. Aerts, G. Groeninckx, Polymer, 40, 6627, 1999.
329. K.B. Migler, E.K. Hobbie, F.Qiao, Polym. Eng. Sci., 39, 2282,1999.
330. B.Lin, U.Sundararaj, F.Mighri, M.A.Erosion, Polym. Eng. Sci., 43,
891, 2003.
331. K. Min, J.L. White, J.F. Fellers, Poly. Eng. Sci., 24, 1327, 1984.
332. Z.K. Walczak,. J. Appl. Polym. Sci., 17,169,1973.
333. H. Potente, S.Krawinkel, M.Bastian, M.Stephan, P.Potschke, J. Appl.
Polym. Sci., 1986, 2001.
334. M.A. Huneault, Z.H. Shi, L.A.Utracki, Polym. Eng. Sci., 35, 115, 1995.
335. P. Martin, J. Devaux, R.Legras, L. Leemans, M.Van Gurp, M.Van
Duin, J. Appl. Polym. Sci., 91,703,2003.
336. J.K. Lee, C.D Han Polymer, 40, 6277, 1999.

Introduction

95

337. H. Potente, M. Bastian, A.Gehring, M. Stephan, P. Potschke, J. Appl.


Polym. Sci., 76, 708, 2000.
338. M. Tjahjadi and J.M. Ottino, J. Fluid Mech., 232, 191, 1991.
339. S.C Jana, M.Tjahjadi, J.M. Ottino, AIChe J.40, 1769, 1994.
340. B.Maxwell, SPEJ., 28,24,1972.
341. J.A. Pathak, M.C. Davis, S.D. Hudson, K.B.Migler, J. Colloid Interface
Sci., 255, 391, 2002.
342. R. Cavallo, S. Duido, M. Simeone, Rheol. Acta, 42, 1, 2003.
343. W. Lerdwijitjarud, R.G.Larson, A. Sirivat, M.J. Solomon, J. Rheol.,
47, 37, 2003.
344. W. Lerdwijitjarud, R.G. Larson, A.Sirivat, Polym. Eng. Sci. 42, 798,
2002.
345. A.Y. Coran, R.P. Patel, J. Karger-Kocsis, Chapman & Hall, London, 2,
pp162, 1995.
346. I. Fortelny, J. Kovar, A.Sikora, Macromol. Chem. 132, 111, 1985.
347. C.E. Scott and C.W. Macosko, Polym. Eng. Sci., 35, 1938, 1995.
348. C.R. Kumar, K.E. George, S.Thomas, J. Appl. Poly. Sci., 61, 2383, 1996.
349. H.G. Fritz, U.Bolz, D.Cai, Polym. Eng. Sci., 39, 1087, 1999.
350. P. Punnarak, S. Tantayanon, V. Tangpasuthadol, Polym. Degrad. Stabil.,
91, 3456,2006.
351. B.G. Soares, M.S.M. Almeida, C. Ranganathaiah, M.V. Deepa U.S.,
Siddaramaiah, Polym.Test., 26,88,2007.
352. F. Shen, X.F. Yuan, C.F. Wu, J. Polym. Sci. Polym. Phys., 45, 41, 2007.

353. X. L. Jiang, X. Xueliang, Polym. Polym. Compo. 15, 145, 2007.